Fertilizers with polyanionic polymers and method of applying polyanionic polymer to plants

ABSTRACT

Novel polyanionic polymers including families of repeat units, such as maleic, itaconic, and sulfonate repeat units. The polymers are at least tetrapolymers and may be in the acid form or as partial or complete salts. The polymers may be synthesized using free radical initiators in the presence of vanadium compounds. The polymers have a variety of uses, particularly in agricultural contexts.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of three provisional applications:Ser. No. 61/870,472, filed Aug. 27, 2013, Ser. No. 61/978,011, filedApr. 10, 2014; and Ser. No. 62/001,110, filed May 21, 2014, all of whichare incorporated herein by reference in their entireties.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention is broadly concerned with a new class ofsubstantially water soluble, biodegradable polyanionic polymers andsyntheses thereof finding particular utility in agricultural uses, e.g.,directly applied to soil, or in combination with fertilizers to increasenutrient uptake; as seed coatings and pesticide adjuvants; to reduceatmospheric ammonia derived from animal manures; as animal feed andwater amendments; and to inhibit nitrification, urease hydrolysis, andphosphate fixation in soils. More particularly, the invention isconcerned with novel polymers that are at least tetrapolymers andpreferably contain specific types of carboxylic and sulfonate repeatunits, as well as methods of synthesizing dicarboxylate/sulfonatepolymers including the novel polymers hereof. Other uses of thepolyanionic polymers are also disclosed, alone or in combination withother polyanionic (e.g., dicarboxylic) polymers and/or other functionalingredients.

2. Description of the Prior Art

For a number of years, Specialty Fertilizer Products, LLC of Leawood,Kans., has commercialized a series of aqueous dispersions ofmaleic-itaconic polymers in partial salt form. These products includeAVAIL® for use with granular and liquid fertilizers (respectively thepartial sodium and ammonium salts), and NUTRISPHERE-N® for use withgranular and liquid fertilizers (the partial calcium salt). For example,such products may be sprayed or otherwise applied to the surface ofsolid fertilizers, such as urea, ammonium salts, monoammonium phosphate(MAP), diammonium phosphate (DAP), potash, and gypsum, or mixed withliquid fertilizers, such as UAN and ammonium polyphosphate.

These prior products have been shown to have a number of outstandingagricultural properties, including the ability to enhance the uptake offertilizer nutrients (e.g., phosphates, nitrogen, potassium, andmicronutrients), to act as adjuvants for pesticides such as glyphosateherbicides, and, when supplemented with an organic drying agent, to veryquickly dry when applied to solid fertilizers, thereby facilitatingproduction of final coated solid fertilizer products. Moreover, thepreferred polymers have been shown to have enhanced activity whenfertilizer formulations containing different types of polymer partialsalts are employed (U.S. Patent Publication No. 2009-0217723). Thistechnology is also described in U.S. Pat. Nos. 6,515,090, 7,655,597,7,736,412, and 8,043,995, and related patents.

Notwithstanding the success of the prior maleic-itaconic polymers,agriculturally useful polymers having even greater activities would bedesirable.

SUMMARY OF THE INVENTION

The present invention overcomes the problems outlined above and providesa new class of polymers preferably having a high carboxylate content andsulfonate repeat units, which are very soluble in water andbiodegradable. As used herein, “polymer” is a broad term, which embraceshomopolymers and copolymers, the latter containing any number ofdifferent repeat units or moieties, such as terpolymers ortetrapolymers. The preferred novel polymers hereof are at leasttetrapolymers having at least four different repeat units distributedalong the lengths of the polymer chains, preferably with at least onerepeat unit each of maleic, itaconic, and sulfonate repeat units. Therepeat units are advantageously derived from corresponding monomers usedin the synthesis of the polymers, and have at least one repeat unit fromeach of three separately defined categories of repeat units, referred toherein as type B, type C, and type G repeat units, and explained indetail below.

The invention has a number of aspects, relating to the new polymers,synthesis of polyanionic polymers, and various uses of the new polymers,alone or in conjunction with other anionic polymers.

1. The New Polymers

The new anionic polymers comprise at least four repeat units distributedalong the length of the polymer chain, the at least four repeat unitsincluding at least one each of type B, type C, and type G repeat units,

-   -   the type B repeat units selected from the group consisting of        repeat units derived from substituted and unsubstituted monomers        of maleic acid and/or anhydride, fumaric acid and/or anhydride,        mesaconic acid and/or anhydride, mixtures of the foregoing, and        any isomers, esters, acid chlorides, and partial or complete        salts of any of the foregoing, wherein type B repeat units may        be substituted with one or more C1-C6 straight or branched chain        alkyl groups substantially free of ring structures and halo        atoms, and wherein the salts have salt-forming cations selected        from the group consisting of metals, amines, and mixtures        thereof,    -   the type C repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted monomers        of itaconic acid, itaconic anhydride, and any isomers, esters,        and the partial or complete salts of any of the foregoing, and        mixtures of any of the foregoing, wherein the type C repeat        units may be substituted with one or more C1-C6 straight or        branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts have        salt-forming cations selected from the group consisting of        metals, amines, and mixtures thereof,    -   the type G repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted        sulfonated monomers possessing at least one carbon-carbon double        bond and at least one sulfonate group and which are        substantially free of aromatic rings and amide groups, and any        isomers, and the partial or complete salts of any of the        foregoing, and mixtures of any of the foregoing, wherein type G        repeat units may be substituted with one or more C1-C6 straight        or branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts of the type G        repeat units have salt-forming cations selected from the group        consisting of metals, amines, and mixtures thereof,    -   at least about 90 mole percent of the repeat units therein are        selected from the group consisting of type B, C, and G repeat        units, and mixtures thereof,    -   the repeat units being randomly located along the polymer,    -   the polymer containing no more than about 10 mole percent of any        of (I) non-carboxylate olefin repeat units, (ii) ether repeat        units, and (iii) non-sulfonated monocarboxylic repeat units.

Preferably, the polymers comprise at least about 96 mole percent of therepeat units therein selected from the group consisting of type B, C,and G repeat units, and mixtures thereof, and still more preferablyconsist essentially of repeat units selected from the group consistingof type B, C, and G repeat units, and mixtures thereof. The polymers arealso substantially free of ester groups and noncarboxylate olefingroups.

Especially preferred polymers have one type B repeat unit, one type Crepeat unit, and two different type G repeat units, especially where theone type B repeat unit is derived from maleic acid, the one type Crepeat unit is derived from itaconic acid, and two type G repeat unitsare respectively derived from methallylsulfonic acid and allylsulfonicacid. In such polymers, the type B repeat unit is present at a level offrom about 35-55 mole percent, the type C repeat unit is present at alevel of from about 20-55 mole percent, the type G repeat unit derivedfrom methallylsulfonic acid is present at a level of from about 1-25mole percent, and the type G repeat unit derived from allylsulfonic acidis present at a level of from about 1-25 mole percent, where the totalamount of all of the repeat units in the polymer is taken as 100 molepercent. Other useful polymers comprise two different type B repeatunits, one type C repeat unit, and one type G repeat unit, and where thepolymer has at least one repeat unit not selected from the groupconsisting of type B, type C, and type G repeat units.

Advantageously, the total amount of type B repeat units in the polymeris from about 1-70 mole percent, the total amount of type C repeat unitsin the polymer is from about 1-80 mole percent, and the total amount oftype G repeat units in the polymer is from about 0.1-65 mole percent,where the total amount of all of the repeat units in the polymer istaken as 100 mole percent. Still more preferably, the total amount oftype B repeat units in the polymer is from about 20-65 mole percent, thetotal amount of type C repeat units in the polymer is from about 15-75mole percent, and the total amount of type G repeat units in the polymeris from about 1-35 mole percent, where the total amount of all of therepeat units in the polymer is taken as 100 mole percent.

The novel polymers generally have a molecular weight of from about800-50,000, and more preferably from about 1000-5000. The polymers ofthe invention may be in a free acid form or in partial or complete saltform, including one or more salt-forming cations bound with the polymer.Such salt-forming cations are usually selected from the group consistingof cations of metals, amines, micronutrients, and mixtures thereof, andespecially those selected from the group consisting of alkali, alkalineearth, and transition metal cations.

The polymers of the invention may be used alone or in combination withanother anionic polymer including maleic and itaconic repeat units.Moreover, polymer-containing formulations may be prepared comprising apolymer in accordance with the invention in combination with one or moreother ingredients, selected from the group consisting of boric acid,boron-containing compounds, boric compound solvents, alcohols, diols,polyols, organic acids, polyvinyl alcohols, dyes, and mixtures thereof.

2. Polymer Synthesis

The invention also provides polymer synthesis methods useful for theproduction of a variety of polymers containing dicarboxylate andsulfonate repeat units, including the novel polymers of the invention.Such methods comprise the steps of:

-   -   forming an aqueous dispersion containing dicarboxylate and        sulfonate repeat unit monomers,    -   the dicarboxylate repeat unit monomers selected from the group        consisting of type B repeat unit monomers, type C repeat unit        monomers, and mixtures thereof,    -   the type B repeat unit monomers selected from the group        consisting of substituted and unsubstituted monomers of maleic        acid and/or anhydride, fumaric acid and/or anhydride, mesaconic        acid and/or anhydride, mixtures of the foregoing, and any        isomers, esters, acid chlorides, and partial or complete salts        of any of the foregoing, wherein type B repeat unit monomers may        be substituted with one or more C1-C6 straight or branched chain        alkyl groups substantially free of ring structures and halo        atoms, and wherein the salts have salt-forming cations selected        from the group consisting of metals, amines, and mixtures        thereof,    -   the type C repeat unit monomers selected from the group        consisting of substituted or unsubstituted monomers of itaconic        acid, itaconic anhydride, and any isomers, esters, and the        partial or complete salts of any of the foregoing, and mixtures        of any of the foregoing, wherein the type C repeat unit monomers        may be substituted with one or more C1-C6 straight or branched        chain alkyl groups substantially free of ring structures and        halo atoms, and wherein the salts have salt-forming cations        selected from the group consisting of metals, amines, and        mixtures thereof,    -   the sulfonate repeat unit monomers selected from the group        consisting of type G repeat unit monomers,    -   the type G repeat unit monomers selected from the group        consisting of substituted or unsubstituted sulfonated monomers        possessing at least one carbon-carbon double bond and at least        one sulfonate group and which are substantially free of aromatic        rings and amide groups, and any isomers, and the partial or        complete salts of any of the foregoing, and mixtures of any of        the foregoing, wherein type G repeat unit monomers may be        substituted with one or more C1-C6 straight or branched chain        alkyl groups substantially free of ring structures and halo        atoms, and wherein the salts of the type G repeat unit monomers        have salt-forming cations selected from the group consisting of        metals, amines, and mixtures thereof;    -   heating the dispersion to an elevated temperature of from about        50−125° C. and adding a vanadium compound to the dispersion; and    -   thereafter adding a free radical initiator comprising at least        about 95% by weight hydrogen peroxide to the dispersion, and        causing the monomers within the dispersion to polymerize in an        oxygen-containing environment until at least about 90% by weight        of the monomers have been converted to the polymer.

In preferred forms, the vanadium compound is added to the dispersionafter the heating step, and the free radical initiator is added over aperiod of from about 30 minutes-24 hours while maintaining thedispersion at the elevated temperature. The free radical initiator alsopreferably consists essentially of hydrogen peroxide. The synthesis isbest carried out with the exclusion of substantial amounts of dissolvediron species and sulfate salts, and in an ambient air environment. Thepolymerization is usually carried out until at least about 98% by weightof the monomers have been converted to the polymer.

In preferred forms, the monomers comprise maleic monomers, itaconicmonomers, allylsulfonate monomers, and methallylsulfonate monomers, andthe vanadium compound is vanadium oxysulfate. The polymers may berecovered in the acid form or be converted to partial or complete salts.

For best results, the type B repeat units are present at a level of lessthan 50 mole percent, and the repeat units are randomly dispersedthroughout the polymer.

In another aspect of the synthesis method, a polymer containingdicarboxylate and sulfonate repeat units may be prepared by a methodcomprising the steps of:

-   -   forming an aqueous dispersion containing dicarboxylate and        sulfonate monomers;    -   heating the dispersion to an elevated temperature of from about        50-125° C. and adding a vanadium compound to the dispersion; and    -   thereafter adding a free radical initiator comprising at least        about 95% by weight hydrogen peroxide to the dispersion, and        causing the monomers within the dispersion to polymerize in an        oxygen-containing environment until at least about 90% by weight        of the monomers have been converted to the polymer.

In preferred forms of this method, the vanadium compound is added to thedispersion after the heating step, and the free radical initiator isadded over a period of from about 30 minutes-24 hours while maintainingthe dispersion at the elevated temperature. The free radical initiatorpreferably consists essentially of hydrogen peroxide, and the dispersionis prepared with the exclusion of substantial amounts of dissolved ironspecies and sulfate salts.

The polymerization is best carried out in an ambient air environments,and until at least about 98% by weight of the monomers have beenconverted to the polymer. The monomers comprise maleic monomers,itaconic monomers, allylsulfonate monomers, and methallylsulfonatemonomers, and the vanadium compound is vanadium oxysulfate. As before,the polymers may be recovered in the acid form or as partial or completesalts.

3. Fertilizer Products

The invention also provides agricultural products and uses thereof,wherein the products comprise fertilizer and a polymer mixed with thefertilizer, the polymer being an anionic polymer comprising at leastfour repeat units distributed along the length of the polymer chain, theat least four repeat units including at least one each of type B, typeC, and type G repeat units,

-   -   the type B repeat units selected from the group consisting of        repeat units derived from substituted and unsubstituted monomers        of maleic acid and/or anhydride, fumaric acid and/or anhydride,        mesaconic acid and/or anhydride, mixtures of the foregoing, and        any isomers, esters, acid chlorides, and partial or complete        salts of any of the foregoing, wherein type B repeat units may        be substituted with one or more C1-C6 straight or branched chain        alkyl groups substantially free of ring structures and halo        atoms, and wherein the salts have salt-forming cations selected        from the group consisting of metals, amines, and mixtures        thereof,    -   the type C repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted monomers        of itaconic acid, itaconic anhydride, and any isomers, esters,        and the partial or complete salts of any of the foregoing, and        mixtures of any of the foregoing, wherein the type C repeat        units may be substituted with one or more C1-C6 straight or        branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts have        salt-forming cations selected from the group consisting of        metals, amines, and mixtures thereof,    -   the type G repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted        sulfonated monomers possessing at least one carbon-carbon double        bond and at least one sulfonate group and which are        substantially free of aromatic rings and amide groups, and any        isomers, and the partial or complete salts of any of the        foregoing, and mixtures of any of the foregoing, wherein type G        repeat units may be substituted with one or more C1-C6 straight        or branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts of the type G        repeat units have salt-forming cations selected from the group        consisting of metals, amines, and mixtures thereof,    -   the anionic polymer containing no more than about 10 mole        percent of non-carboxylate olefins and/or ethers.

The fertilizer may be a solid fertilizer, and particularly granular, andthe polymer is applied to the fertilizer as a liquid dispersion.Alternately, the fertilizer may be in liquid form, and the polymer ismixed with the liquid fertilizer. The fertilizers are preferablyselected from the group consisting of starter fertilizers,phosphate-based fertilizers, fertilizers containing nitrogen,phosphorus, potassium, calcium, magnesium, boron, zinc, manganese,copper, or molybdenum materials. One especially preferred solidfertilizer is urea. Where the fertilizers are solid, the polymers ispreferably present at a level of from about 0.001-20 g per 100 g of thefertilizer. The tetrapolymers of the invention may be used alone or incombination with another anionic polymer including maleic and itaconicrepeat units.

More generally, the invention provides agricultural products comprisingfertilizer and a polymer mixed with the fertilizer, the polymer being ananionic polymer comprising at least four repeat units distributed alongthe length of the polymer chain, and the repeat units include at leastone each of a maleic, itaconic, and sulfonate repeat unit. Mostpreferably the polymer is a tetrapolymer and having maleic and itaconicrepeat units, and two different sulfonate repeat units. The polymers maybe recovered in the free acid form or as partial or complete salts, andin preferred forms include an amount of a micronutrient that ispreferably bound or complexed with the polymer.

All of the fertilizer/polymer products of the invention may be used byapplying such products to soil.

4. Pesticide Products

The invention provides pesticide products comprising a pesticide and apolymer, the polymer being an anionic polymer comprising at least fourrepeat units distributed along the length of the polymer chain, the atleast four repeat units including at least one each of type B, type C,and type G repeat units,

-   -   the type B repeat units selected from the group consisting of        repeat units derived from substituted and unsubstituted monomers        of maleic acid and/or anhydride, fumaric acid and/or anhydride,        mesaconic acid and/or anhydride, mixtures of the foregoing, and        any isomers, esters, acid chlorides, and partial or complete        salts of any of the foregoing, wherein type B repeat units may        be substituted with one or more C1-C6 straight or branched chain        alkyl groups substantially free of ring structures and halo        atoms, and wherein the salts have salt-forming cations selected        from the group consisting of metals, amines, and mixtures        thereof,    -   the type C repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted monomers        of itaconic acid, itaconic anhydride, and any isomers, esters,        and the partial or complete salts of any of the foregoing, and        mixtures of any of the foregoing, wherein the type C repeat        units may be substituted with one or more C1-C6 straight or        branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts have        salt-forming cations selected from the group consisting of        metals, amines, and mixtures thereof,    -   the type G repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted        sulfonated monomers possessing at least one carbon-carbon double        bond and at least one sulfonate group and which are        substantially free of aromatic rings and amide groups, and any        isomers, and the partial or complete salts of any of the        foregoing, and mixtures of any of the foregoing, wherein type G        repeat units may be substituted with one or more C1-C6 straight        or branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts of the type G        repeat units have salt-forming cations selected from the group        consisting of metals, amines, and mixtures thereof,    -   the anionic polymer containing no more than about 10 mole        percent of non-carboxylate olefins and/or ethers.

A wide variety of pesticides may be used in these products, such asthose selected from the group consisting of herbicides, insecticides,fungicides and nematocides. The complete product may be in solid, liquidor aerosol form, and may also include another polymer including maleicand itaconic repeat units. The polymers may be in acid form, or aspartial or complete salts.

More generally, the invention provides pesticide products comprising apesticide and a polymer, the polymer being an anionic polymer comprisingat least four repeat units distributed along the length of the polymerchain, the repeat units including at least one each of a maleic,itaconic, and sulfonate repeat unit.

Particularly preferred compositions comprise a polymer mixed withglyphosate and micronutrients, the polymer being an anionic polymercomprising at least four repeat units distributed along the length ofthe polymer chain, the repeat units including at least one each of amaleic, itaconic, and sulfonate repeat unit. Again, the polymers ofthese compositions may be in combination with another anionic polymerincluding maleic and itaconic repeat units, and the micronutrients maybe complexed with the polymer. The polymers may be in acid form, or aspartial or complete salts.

All of the pesticide products of the invention may be used in pesticidalmethods comprising the step of applying the products to soil, hardsurfaces, or the leaves of plants.

5. Sulfur Products

The invention further provides products comprising a compound selectedfrom the group consisting of gypsum, one or more members of theKieserite Group, potassium magnesium sulfate, elemental sulfur, andmixtures thereof, and a polymer, the polymer being an anionic polymercomprising at least four repeat units distributed along the length ofthe polymer chain,

-   -   the at least four repeat units including at least one each of        type B, type C, and type G repeat units, the type B repeat units        selected from the group consisting of repeat units derived from        substituted and unsubstituted monomers of maleic acid and/or        anhydride, fumaric acid and/or anhydride, mesaconic acid and/or        anhydride, mixtures of the foregoing, and any isomers, esters,        acid chlorides, and partial or complete salts of any of the        foregoing, wherein type B repeat units may be substituted with        one or more C1-C6 straight or branched chain alkyl groups        substantially free of ring structures and halo atoms, and        wherein the salts have salt-forming cations selected from the        group consisting of metals, amines, and mixtures thereof,    -   the type C repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted monomers        of itaconic acid, itaconic anhydride, and any isomers, esters,        and the partial or complete salts of any of the foregoing, and        mixtures of any of the foregoing, wherein the type C repeat        units may be substituted with one or more C1-C6 straight or        branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts have        salt-forming cations selected from the group consisting of        metals, amines, and mixtures thereof,    -   the type G repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted        sulfonated monomers possessing at least one carbon-carbon double        bond and at least one sulfonate group and which are        substantially free of aromatic rings and amide groups, and any        isomers, and the partial or complete salts of any of the        foregoing, and mixtures of any of the foregoing, wherein type G        repeat units may be substituted with one or more C1-C6 straight        or branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts of the type G        repeat units have salt-forming cations selected from the group        consisting of metals, amines, and mixtures thereof,    -   the anionic polymer containing no more than about 10 mole        percent of non-carboxylate olefins and/or ethers.

Preferably, the compound comprises gypsum, and the polymer is present ata level of from about 0.01-10% w/w (more preferably from about 0.05-2%w/w), where the total weight of the polymer and the compound is taken as100% by weight. At least about 80 mole percent of the polymer repeatunits contain at least one anionic group. More preferably, the polymerhas from about 1-70 mole percent of the type B repeat units, from about15-75 mole percent of the type C repeat units, and from about 0.1-65mole percent of the type G repeat units, and the total abundance of thetype B, C, and G repeat units being at least about 90 mole percent. Thepolymer may have a molecular weight from about 800-50,000.

More generally, the products of this aspect of the invention comprise acompound selected from the group consisting of gypsum, one or moremembers of the Kieserite Group, potassium magnesium sulfate, elementalsulfur, and mixtures thereof, and a polymer, the polymer being ananionic polymer comprising at least four repeat units distributed alongthe length of the polymer chain, the repeat units including at least oneeach of a maleic, itaconic, and sulfonate repeat unit.

The sulfur products of the invention are used to fertilize soil byapplying the products to soil.

6. Liquid or Solutionized Fertilizer Products

In another aspect of the invention, liquid or solutionized fertilizerproducts (e.g., gypsum or UAN) are provided including a fertilizer inaqueous dispersion, and a polyanionic polymer comprising at least fourrepeat units distributed along the length of the polymer chain, therepeat units including at least one each of a maleic, itaconic, andsulfonic repeat unit, and an amount of an alpha-hydroxy acidformulation. The fertilizer product normally is an aqueous dispersionhaving a pH of from about 4-7, or from about 0.5-3.

Preferably, the alpha-hydroxy acids are saturated and essentially freeof double bonds and carbon ring structures, and are selected from thegroup consisting of lactic acid, glycolic acid, citric acid, tartaricacid, tartronic acid, glyceric acid, and dihydroxypropanedioic acid, andmixtures thereof.

Overall, the fertilizer products preferably contain from about 10-45%w/w of the polymer, from about 3-60% w/w of the alpha-hydroxy acid, withthe balance being solvent. The polymer advantageously has at least fourrepeat units distributed along the length of the polymer chain, therepeat units including at least one each of a maleic, itaconic, andsulfonate repeat unit. In particularly preferred forms, the polymercomprises at least four repeat units including at least one each of typeB, type C, and type G repeat units,

-   -   the type B repeat units selected from the group consisting of        repeat units derived from substituted and unsubstituted monomers        of maleic acid and/or anhydride, fumaric acid and/or anhydride,        mesaconic acid and/or anhydride, mixtures of the foregoing, and        any isomers, esters, acid chlorides, and partial or complete        salts of any of the foregoing, wherein type B repeat units may        be substituted with one or more C1-C6 straight or branched chain        alkyl groups substantially free of ring structures and halo        atoms, and wherein the salts have salt-forming cations selected        from the group consisting of metals, amines, and mixtures        thereof,    -   the type C repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted monomers        of itaconic acid, itaconic anhydride, and any isomers, esters,        and the partial or complete salts of any of the foregoing, and        mixtures of any of the foregoing, wherein the type C repeat        units may be substituted with one or more C1-C6 straight or        branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts have        salt-forming cations selected from the group consisting of        metals, amines, and mixtures thereof,    -   the type G repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted        sulfonated monomers possessing at least one carbon-carbon double        bond and at least one sulfonate group and which are        substantially free of aromatic rings and amide groups, and any        isomers, and the partial or complete salts of any of the        foregoing, and mixtures of any of the foregoing, wherein type G        repeat units may be substituted with one or more C1-C6 straight        or branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts of the type G        repeat units have salt-forming cations selected from the group        consisting of metals, amines, and mixtures thereof,    -   at least about 90 mole percent of the repeat units therein are        selected from the group consisting of type B, C, and G repeat        units, and mixtures thereof,    -   the repeat units being randomly located along the polymer,    -   the polymer containing no more than about 10 mole percent of any        of (I) non-carboxylate olefin repeat units, (ii) ether repeat        units, and (iii) non-sulfonated monocarboxylic repeat units.

The fertilizer products of the invention may also be improved by thepresence of an amount of a polyvinyl alcohol (PVA) therein, especiallyat a level of from about 0.1-10% w/w. Moreover, a plurality of differentPVAs may be employed. The PVA should have a hydrolysis level of at leastabout 97 mole percent. The products may also include another polymerhaving maleic and itaconic repeat units therein.

The liquid or solutionized products of the invention are used byapplying such products to soil.

7. Potassium Products

The invention in another aspect provides potassium products comprisingat least partially water soluble potassium-containing solids, e.g.,potassium chloride, having thereon the dried residue of an aqueousadditive comprising a polymer salt containing a plurality of anionicrepeat units including maleic and itaconic repeat units, withsubstantially all of the salt-forming cations of the polymer salt beingalkali metal cations, the aqueous additive having a pH of from about0.1-4 (more preferably from about 0.5-3, and most preferably about 1).The polymer is preferably present on the surface of thepotassium-containing solids at a level of from about 0.001-10% byweight, based upon the total weight of the product taken as 100% byweight. The aqueous additive may also contain a carboxymethyl cellulosesalt.

The polymer is advantageously at least a tetrapolymer and comprises atleast four repeat units distributed along the polymer chain, the repeatunits including at least one each of a maleic, itaconic, and sulfonaterepeat unit. More preferably, the polymer as at least one each of typeB, type C, and type G repeat units,

-   -   the type B repeat units selected from the group consisting of        repeat units derived from substituted and unsubstituted monomers        of maleic acid and/or anhydride, fumaric acid and/or anhydride,        mesaconic acid and/or anhydride, mixtures of the foregoing, and        any isomers, esters, acid chlorides, and partial or complete        salts of any of the foregoing, wherein type B repeat units may        be substituted with one or more C1-C6 straight or branched chain        alkyl groups substantially free of ring structures and halo        atoms, and wherein the salts have salt-forming cations selected        from the group consisting of metals, amines, and mixtures        thereof,    -   the type C repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted monomers        of itaconic acid, itaconic anhydride, and any isomers, esters,        and the partial or complete salts of any of the foregoing, and        mixtures of any of the foregoing, wherein the type C repeat        units may be substituted with one or more C1-C6 straight or        branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts have        salt-forming cations selected from the group consisting of        metals, amines, and mixtures thereof,    -   the type G repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted        sulfonated monomers possessing at least one carbon-carbon double        bond and at least one sulfonate group and which are        substantially free of aromatic rings and amide groups, and any        isomers, and the partial or complete salts of any of the        foregoing, and mixtures of any of the foregoing, wherein type G        repeat units may be substituted with one or more C1-C6 straight        or branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts of the type G        repeat units have salt-forming cations selected from the group        consisting of metals, amines, and mixtures thereof,    -   at least about 90 mole percent of the repeat units therein are        selected from the group consisting of type B, C, and G repeat        units, and mixtures thereof,    -   the repeat units being randomly located along the polymer,    -   the polymer containing no more than about 10 mole percent of any        of (I) non-carboxylate olefin repeat units, (ii) ether repeat        units, and (iii) non-sulfonated monocarboxylic repeat units.

Preferably, at least about 96 mole percent of the repeat units thereinare selected from the group consisting of type B, C, and G repeat units,and mixtures thereof, and still more preferably the repeat units consistessentially of repeat units selected from the group consisting of typeB, C, and G repeat units, and mixtures thereof; for best results, thepolymer is substantially free of ester and noncarboxylate olefin groups.

In another aspect, the polymer has one type B repeat unit, one type Crepeat unit, and two different type G repeat units, is at least atetrapolymer, and the one type B repeat unit is derived from maleicacid, the one type C repeat unit is derived from itaconic acid, and thetwo type G repeat units are respectively derived from methallylsulfonicacid and allylsulfonic acid.

More generally, the invention provides potassium products comprising atleast partially water soluble potassium-containing solids having thereonthe dried residue of an aqueous additive comprising a polymer includingat least four repeat units distributed along the polymer chain, therepeat units including at least one each of a maleic, itaconic, andsulfonate repeat unit.

The polymers of the invention may be in the acid form or as partial orcomplete salts of alkali metals. The polymers are normally in the formof aqueous dispersions and are as such applied to the potassium solids,followed by drying thereof, so that the polymer is in the form of adried residue. The potassium products of the invention may be used byapplying the products to soil.

8. Seed Products

Improved coated seed products are also a part of the invention andcomprise an agricultural seed coated with a polymer composition, thepolymer composition including an anionic polymer comprising at leastfour repeat units distributed along the length of the polymer chain, theat least four repeat units including at least one each of type B, typeC, and type G repeat units,

-   -   the type B repeat units selected from the group consisting of        repeat units derived from substituted and unsubstituted monomers        of maleic acid and/or anhydride, fumaric acid and/or anhydride,        mesaconic acid and/or anhydride, mixtures of the foregoing, and        any isomers, esters, acid chlorides, and partial or complete        salts of any of the foregoing, wherein type B repeat units may        be substituted with one or more C1-C6 straight or branched chain        alkyl groups substantially free of ring structures and halo        atoms, and wherein the salts have salt-forming cations selected        from the group consisting of metals, amines, and mixtures        thereof,    -   the type C repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted monomers        of itaconic acid, itaconic anhydride, and any isomers, esters,        and the partial or complete salts of any of the foregoing, and        mixtures of any of the foregoing, wherein the type C repeat        units may be substituted with one or more C1-C6 straight or        branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts have        salt-forming cations selected from the group consisting of        metals, amines, and mixtures thereof,    -   the type G repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted        sulfonated monomers possessing at least one carbon-carbon double        bond and at least one sulfonate group and which are        substantially free of aromatic rings and amide groups, and any        isomers, and the partial or complete salts of any of the        foregoing, and mixtures of any of the foregoing, wherein type G        repeat units may be substituted with one or more C1-C6 straight        or branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts of the type G        repeat units have salt-forming cations selected from the group        consisting of metals, amines, and mixtures thereof,    -   the anionic polymer containing no more than about 10 mole        percent of non-carboxylate olefins and/or ethers.

The polymer composition is present in the seed product at a level offrom about 0.001-10% by weight, based upon the total weight of thecoated seed product. Preferably, at least about 96 mole percent of therepeat units in the polymer are selected from the group consisting oftype B, C, and G repeat units, and mixtures thereof, and most preferablythe repeat units consist essentially of repeat units selected from thegroup consisting of type B, C, and G repeat units, and mixtures thereof;also, it is preferred that the polymers be substantially free of esterand noncarboxylate olefin groups. Particularly advantageous polymershave one type B repeat unit, one type C repeat unit, and two differenttype G repeat units, and especially where the polymer is a tetrapolymer,the one type B repeat unit is derived from maleic acid, the one type Crepeat unit is derived from itaconic acid, and two type G repeat unitsare respectively derived from methallylsulfonic acid and allylsulfonicacid.

Certain preferred polymers have type B repeat unit present at a level offrom about 35-50 mole percent, the type C repeat unit present at a levelof from about 20-55 mole percent, the type G repeat unit derived frommethallylsulfonic acid being present at a level of from about 1-25 molepercent, and the type G repeat unit derived from allylsulfonic acidbeing present at a level of from about 1-20 mole percent, where thetotal amount of all of the repeat units in the polymer is taken as 100mole percent.

The polymers useful in the invention may be in acid form or as partialor complete salts, particularly of micronutrient metals (e.g., Zn, Mn,B, Fe, Mo, Cu, and mixtures thereof). More generally, the inventionprovides an agricultural seed coated with a polymer composition, thepolymer composition including an anionic polymer comprising at leastfour repeat units distributed along the length of the polymer chain, therepeat units including at least one each of a maleic, itaconic, andsulfonate repeat unit.

In preparing the seed products of the invention, the polymer isinitially applied to the seed as an aqueous composition, preferablyhaving a pH of from about 5-7.

9. Methods of Reducing Atmospheric Ammonia

The invention additionally provides a method of reducing atmosphericammonia by applying a polymer composition in an area subject toevolution of ammonia, the polymer composition including an anionicpolymer comprising at least four repeat units distributed along thelength of the polymer chain, the repeat units including at least oneeach of a maleic, itaconic, and sulfonate repeat unit. The area may be alivestock or poultry confinement facility including a manure collectionzone, upright walls forming an enclosure, and a roof substantiallycovering the zone, and in such cases, the polymer composition may beapplied directly to the manure within the collection zone. The polymercomposition is preferably applied at a level of from about 0.005-3gallons per ton of manure, in the form of an aqueous dispersion having apH of from about 1-5. If desired, another polymer may be used incombination with the anionic polymer and including maleic and itaconicrepeat units. The polymers of the invention may be in the form of apartial or complete salt, particularly a calcium and/or ammonium partialsalt. Moreover, certain preferred polymer compositions include a firstpolymer in the form of a partial salt of calcium, and a second polymerin the form of a partial salt of ammonium.

Most preferably, the repeat units of the polymer include at least oneeach of type B, type C, and type G repeat units,

-   -   the type B repeat units selected from the group consisting of        repeat units derived from substituted and unsubstituted monomers        of maleic acid and/or anhydride, fumaric acid and/or anhydride,        mesaconic acid and/or anhydride, mixtures of the foregoing, and        any isomers, esters, acid chlorides, and partial or complete        salts of any of the foregoing, wherein type B repeat units may        be substituted with one or more C1-C6 straight or branched chain        alkyl groups substantially free of ring structures and halo        atoms, and wherein the salts have salt-forming cations selected        from the group consisting of metals, amines, and mixtures        thereof,    -   the type C repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted monomers        of itaconic acid, itaconic anhydride, and any isomers, esters,        and the partial or complete salts of any of the foregoing, and        mixtures of any of the foregoing, wherein the type C repeat        units may be substituted with one or more C1-C6 straight or        branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts have        salt-forming cations selected from the group consisting of        metals, amines, and mixtures thereof,    -   the type G repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted        sulfonated monomers possessing at least one carbon-carbon double        bond and at least one sulfonate group and which are        substantially free of aromatic rings and amide groups, and any        isomers, and the partial or complete salts of any of the        foregoing, and mixtures of any of the foregoing, wherein type G        repeat units may be substituted with one or more C1-C6 straight        or branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts of the type G        repeat units have salt-forming cations selected from the group        consisting of metals, amines, and mixtures thereof,    -   at least about 90 mole percent of the repeat units therein are        selected from the group consisting of type B, C, and G repeat        units, and mixtures thereof,    -   the repeat units being randomly located along the polymer,    -   the polymer containing no more than about 10 mole percent of any        of (I) non-carboxylate olefin repeat units, (ii) ether repeat        units, and (iii) non-sulfonated monocarboxylic repeat units.

This polymer preferably has at least about 96 mole percent of the repeatunits therein selected from the group consisting of type B, C, and Grepeat units, and mixtures thereof, and most preferably consistsessentially of repeat units selected from the group consisting of typeB, C, and G repeat units, and mixtures thereof. These polymers arepreferably substantially free of ester and noncarboxylate olefin groups.One preferred polymer has one type B repeat unit, one type C repeatunit, and two different type G repeat units. In this case, the polymeris preferably a tetrapolymer with the one type B repeat unit derivedfrom maleic acid, the one type C repeat unit derived from itaconic acid,and the two type G repeat units respectively derived frommethallylsulfonic acid and allylsulfonic acid. Furthermore, the type Brepeat unit is present at a level of from about 35-50 mole percent, thetype C repeat unit is present at a level of from about 20-55 molepercent, the type G repeat unit derived from methallylsulfonic acid ispresent at a level of from about 1-25 mole percent, and the type Grepeat unit derived from allylsulfonic acid being present at a level offrom about 1-20 mole percent, where the total amount of all of therepeat units in the polymer is taken as 100 mole percent.

Additional preferred compositions are operable to reduce atmosphereammonia by application of the composition to an area subject toevolution of ammonia, with such composition comprising a first polymercomposition comprising a first anionic polymer having at least fourrepeat units distributed along the length of the polymer chain, therepeat units including at least one each of a maleic, itaconic, andsulfonate repeat unit, the first anionic polymer being in the form of apartial or complete salt of calcium; and a second polymer compositioncomprising a second anionic polymer having maleic and itaconic repeatunits along the length of the polymer chain, the second anionic polymerbeing a partial or complete salt of ammonium. Such polymers preferablyare each in the form of an aqueous dispersion and have at least fourrepeat units distributed along the length of the polymer chain, therepeat units including at least one each of a maleic, itaconic, andsulfonate repeat unit.

10. Improved Animal Feeds and Waters

Improved animal feeds are provided comprising quantities of feedingredients normally fed to the animal, and an amount of a feedamendment including a partial or complete polymer salt, the amount ofthe amendment sufficient to reduce volatilized ammonia derived from theexcrement of the animal fed the improved animal feed, as compared withthe volatilized ammonia of an animal fed an identical feed, without theamendment. The polymer salts of the invention are usually in the form ofaqueous dispersions having a pH of from about 1-5 and comprise at leastfour repeat units distributed along the length of the polymer chain, therepeat units including at least one each of a maleic, itaconic, andsulfonate repeat unit.

In preferred forms, the at least four repeat units include at least oneeach of type B, type C, and type G repeat units,

-   -   the type B repeat units selected from the group consisting of        repeat units derived from substituted and unsubstituted monomers        of maleic acid and/or anhydride, fumaric acid and/or anhydride,        mesaconic acid and/or anhydride, mixtures of the foregoing, and        any isomers, esters, acid chlorides, and partial or complete        salts of any of the foregoing, wherein type B repeat units may        be substituted with one or more C1-C6 straight or branched chain        alkyl groups substantially free of ring structures and halo        atoms, and wherein the salts have salt-forming cations selected        from the group consisting of metals, amines, and mixtures        thereof,    -   the type C repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted monomers        of itaconic acid, itaconic anhydride, and any isomers, esters,        and the partial or complete salts of any of the foregoing, and        mixtures of any of the foregoing, wherein the type C repeat        units may be substituted with one or more C1-C6 straight or        branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts have        salt-forming cations selected from the group consisting of        metals, amines, and mixtures thereof,    -   the type G repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted        sulfonated monomers possessing at least one carbon-carbon double        bond and at least one sulfonate group and which are        substantially free of aromatic rings and amide groups, and any        isomers, and the partial or complete salts of any of the        foregoing, and mixtures of any of the foregoing, wherein type G        repeat units may be substituted with one or more C1-C6 straight        or branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts of the type G        repeat units have salt-forming cations selected from the group        consisting of metals, amines, and mixtures thereof,    -   at least about 90 mole percent of the repeat units therein are        selected from the group consisting of type B, C, and G repeat        units, and mixtures thereof,    -   the repeat units being randomly located along the polymer,    -   the polymer salt containing no more than about 10 mole percent        of any of (I) non-carboxylate olefin repeat units, (ii) ether        repeat units, and (iii) non-sulfonated monocarboxylic repeat        units.

Advantageously, at least about 96 mole percent of the repeat unitstherein are selected from the group consisting of type B, C, and Grepeat units, and mixtures thereof, and even more preferably the repeatunits consist essentially of type B, C, and G repeat units, and mixturesthereof; moreover, the polymers are preferably substantially free ofester and noncarboxylate olefin groups.

Specially preferred polymer salts have one type B repeat unit, one typeC repeat unit, and two different type G repeat units, and, when in theform of a tetrapolymer, the one type B repeat unit is derived frommaleic acid, the one type C repeat unit is derived from itaconic acid,and the two type G repeat units are respectively derived frommethallylsulfonic acid and allylsulfonic acid. These polymer saltspreferably have the type B repeat unit being present at a level of fromabout 35-50 mole percent, the type C repeat unit being present at alevel of from about 20-55 mole percent, the type G repeat unit derivedfrom methallylsulfonic acid being present at a level of from about 1-25mole percent, and the type G repeat unit derived from allylsulfonic acidbeing present at a level of from about 1-20 mole percent, where thetotal amount of all of the repeat units in the polymer is taken as 100mole percent.

In many cases, two separate polymer salts are used, one being a partialsalt of calcium, and the other being a partial salt of ammonium.Moreover, other, different polymers including maleic and itaconic repeatunits may be used in the amendments of the invention.

The animal feeds of the invention may be used as a method of reducingvolatilized ammonia derived from the excrement of animals, comprisingthe step of administering to (feeding) the animals one or more of theabove-described feeds.

Similarly, the invention also provides improved animal waters comprisinga mixture of water and a partial or complete polymer salt, the polymersalt being in an amount sufficient to reduce volatilized ammonia derivedfrom the excrement of the animal fed the improved animal water, ascompared with the volatilized ammonia of an animal fed an identicalwater, without the amendment. The polymer salts preferably are in theform of aqueous dispersions having a pH of from about 1-5, and compriseat least four repeat units distributed along the length of the polymerchain, the repeat units including at least one each of a maleic,itaconic, and sulfonate repeat unit.

The at least four repeat units preferably include at least one each oftype B, type C, and type G repeat units,

-   -   the type B repeat units selected from the group consisting of        repeat units derived from substituted and unsubstituted monomers        of maleic acid and/or anhydride, fumaric acid and/or anhydride,        mesaconic acid and/or anhydride, mixtures of the foregoing, and        any isomers, esters, acid chlorides, and partial or complete        salts of any of the foregoing, wherein type B repeat units may        be substituted with one or more C1-C6 straight or branched chain        alkyl groups substantially free of ring structures and halo        atoms, and wherein the salts have salt-forming cations selected        from the group consisting of metals, amines, and mixtures        thereof,    -   the type C repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted monomers        of itaconic acid, itaconic anhydride, and any isomers, esters,        and the partial or complete salts of any of the foregoing, and        mixtures of any of the foregoing, wherein the type C repeat        units may be substituted with one or more C1-C6 straight or        branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts have        salt-forming cations selected from the group consisting of        metals, amines, and mixtures thereof,    -   the type G repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted        sulfonated monomers possessing at least one carbon-carbon double        bond and at least one sulfonate group and which are        substantially free of aromatic rings and amide groups, and any        isomers, and the partial or complete salts of any of the        foregoing, and mixtures of any of the foregoing, wherein type G        repeat units may be substituted with one or more C1-C6 straight        or branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts of the type G        repeat units have salt-forming cations selected from the group        consisting of metals, amines, and mixtures thereof,    -   at least about 90 mole percent of the repeat units therein are        selected from the group consisting of type B, C, and G repeat        units, and mixtures thereof,    -   the repeat units being randomly located along the polymer,    -   the polymer salt containing no more than about 10 mole percent        of any of (I) non-carboxylate olefin repeat units, (ii) ether        repeat units, and (iii) non-sulfonated monocarboxylic repeat        units.

Advantageously, at least about 96 mole percent of the repeat unitstherein are selected from the group consisting of type B, C, and Grepeat units, and mixtures thereof, and more preferably the repeat unitsconsist essentially of the type B, C, and G repeat units, and mixturesthereof; the polymers are also preferably substantially free of esterand noncarboxylate olefin groups.

In one preferred case, the polymer salt has one type B repeat unit, onetype C repeat unit, and two different type G repeat units, andespecially where the polymer salt is a tetrapolymer, the one type Brepeat unit is derived from maleic acid, the one type C repeat unit isderived from itaconic acid, and the two type G repeat units arerespectively derived from methallylsulfonic acid and allylsulfonic acid.The type B repeat unit is preferably present at a level of from about35-50 mole percent, the type C repeat unit being present at a level offrom about 20-55 mole percent, the type G repeat unit derived frommethallylsulfonic acid being present at a level of from about 1-25 molepercent, and the type G repeat unit derived from allylsulfonic acidbeing present at a level of from about 1-20 mole percent, where thetotal amount of all of the repeat units in the polymer is taken as 100mole percent.

The polymers of the invention are preferably in the form of partialsalts, and the overall compositions may comprise two separate polymersalts, one polymer salt being a partial salt of calcium, and the otherpolymer salt being a partial salt of ammonium.

11. Methods of Improving Soil Conditions

The invention provides methods of inhibiting a soil condition selectedfrom the group consisting of nitrification processes, phosphate fixationprocesses, urease activities, and combinations thereof, comprising thestep of applying to soil an effective amount of an anionic polymerincluding at least four repeat units distributed along the length of thepolymer chain, the repeat units including at least one each of a maleic,itaconic, and sulfonate repeat units. The repeat units preferablyinclude at least one each of type B, type C, and type G repeat units,

-   -   the type B repeat units selected from the group consisting of        repeat units derived from substituted and unsubstituted monomers        of maleic acid and/or anhydride, fumaric acid and/or anhydride,        mesaconic acid and/or anhydride, mixtures of the foregoing, and        any isomers, esters, acid chlorides, and partial or complete        salts of any of the foregoing, wherein type B repeat units may        be substituted with one or more C1-C6 straight or branched chain        alkyl groups substantially free of ring structures and halo        atoms, and wherein the salts have salt-forming cations selected        from the group consisting of metals, amines, and mixtures        thereof,    -   the type C repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted monomers        of itaconic acid, itaconic anhydride, and any isomers, esters,        and the partial or complete salts of any of the foregoing, and        mixtures of any of the foregoing, wherein the type C repeat        units may be substituted with one or more C1-C6 straight or        branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts have        salt-forming cations selected from the group consisting of        metals, amines, and mixtures thereof,    -   the type G repeat units selected from the group consisting of        repeat units derived from substituted or unsubstituted        sulfonated monomers possessing at least one carbon-carbon double        bond and at least one sulfonate group and which are        substantially free of aromatic rings and amide groups, and any        isomers, and the partial or complete salts of any of the        foregoing, and mixtures of any of the foregoing, wherein type G        repeat units may be substituted with one or more C1-C6 straight        or branched chain alkyl groups substantially free of ring        structures and halo atoms, and wherein the salts of the type G        repeat units have salt-forming cations selected from the group        consisting of metals, amines, and mixtures thereof,    -   at least about 90 mole percent of the repeat units therein are        selected from the group consisting of type B, C, and G repeat        units, and mixtures thereof,    -   the repeat units being randomly located along the polymer,    -   the polymer containing no more than about 10 mole percent of any        of (I) non-carboxylate olefin repeat units, (ii) ether repeat        units, and (iii) non-sulfonated monocarboxylic repeat units.

Advantageously, at least about 96 mole percent of the repeat unitstherein are selected from the group consisting of type B, C, and Grepeat units, and mixtures thereof, and more preferably the repeat unitsconsist essentially of type B, C, and G repeat units, and mixturesthereof; the polymers are substantially free of ester and noncarboxylateolefin groups.

In one particular case, the polymer has one type B repeat unit, one typeC repeat unit, and two different type G repeat units; especially wherethe polymer is a tetrapolymer, the one type B repeat unit is derivedfrom maleic acid, the one type C repeat unit is derived from itaconicacid, and two type G repeat units are respectively derived frommethallylsulfonic acid and allylsulfonic acid.

In preferred forms, the type B repeat unit is present at a level of fromabout 35-50 mole percent, the type C repeat unit being present at alevel of from about 20-55 mole percent, the type G repeat unit derivedfrom methallylsulfonic acid being present at a level of from about 1-25mole percent, and the type G repeat unit derived from allylsulfonic acidbeing present at a level of from about 1-20 mole percent, where thetotal amount of all of the repeat units in the polymer is taken as 100mole percent.

In carrying out the invention, the anionic polymer is mixed with anammoniacal solid, liquid, or gaseous fertilizer, and especially solidfertilizers; in the latter case, the polymer is applied to the surfaceof the fertilizer as an aqueous dispersion followed by drying, so thatthe polymer is present on the solid fertilizer as a dried residue. Thepolymer is generally applied at a level of from about 0.01-10% byweight, based upon the total weight of the polymer/fertilizer producttaken as 100% by weight. Where the fertilizer is an aqueous liquidfertilizer, the polymer is added thereto with mixing.

The polymers of the invention are preferably in aqueous dispersion andhave a pH of up to about 3. These polymers may be used alone or incombination with another anionic polymer including maleic and itaconicrepeat units.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The Novel Polymers ofthe Invention

The novel polyanionic polymers of the present invention (sometimesreferred to herein as “Class I” polymers) are at least tetrapolymers,i.e., they are composed of at least four different repeat unitsindividually and independently selected from the group consisting oftype B, type C, and type G repeat units, and mixtures thereof, describedin detail below. However, the polymers comprehend polymers having morethan four distinct repeat units, with the excess repeat units beingselected from the group consisting of type B, type C, and type G repeatunits, and mixtures thereof, as well as other monomers or repeat unitsnot being type B, C, or G repeat units.

Preferred polymers contain at least one repeat unit from each of the B,C, and G types, one other repeat unit selected from the group consistingof type B, type C, and type G repeat units, and optionally other repeatunits not selected from type B, type C, and type G repeat units.Particularly preferred polymers comprise a single type B repeat unit, asingle type C repeat unit, and two different type G repeat units, or twodifferent type B repeat units, a single type C repeat unit, and one ormore different type G repeat units.

However constituted, preferred polymers contain at least about 90 molepercent (more preferably at least about 96 mole percent) of repeat unitsselected from the group consisting of type B, C, and G repeat units(i.e., the polymers should contain no more than about 10 mole percent(preferably no more than about 4 mole percent) of repeat units notselected from types B, C, and G). The most preferred final polymersshould be substantially free of ester groups (i.e., no more than about 5mole percent ester groups, more preferably no more than about 1 molepercent).

The polymers may be converted to a wide range of salts, whether fullysaturated (wherein all anionic groups are paired with a suitable cation,e.g., a metal or amine) or partial (wherein not all anionic groups areso paired), and may be made using either a single cation (e.g., sodium),or using any number of different cations at any level (e.g., mixedsodium and ammonium cations). Metal cations can be simple cations suchas sodium or calcium, but more complex cations can also be used, such ascations containing a metal atom and other atom(s) as well, e.g., vanadylcations. Among preferred metal cations (to be used alone or as mixedsalts) are those derived from alkali, alkaline earth, and transitionmetals. The polymers may also be in the form of amine partial orcomplete salts (as used herein, “amines” refers to primary, secondary,or tertiary amines, monoamines, diamines, and triamines, as well asammonia, ammonium ions, quaternary amines, quaternary ammonium ions,alkanolamines (e.g., ethanolamine, diethanolamine, and triethanolamine),and tetraalkylammonium species). The most preferred class of amines arealkyl amines, where the alkyl group(s) have from 1-30 carbon atoms andare of straight or branched chain configuration. Such amines should beessentially free of aromatic rings (no more than about 5 mole percentaromatic rings, and more preferably no more than about 1 mole percentthereof). A particularly suitable alkyl amine is isopropylamine.

The degree of cation substitution and the identity of cation(s) may bevaried completely independently of each other. This flexibility allowsproduction of many different full or partial salt polymers of desirableproperties. The solubility and other properties of the polymers can bemodified by judicious selection of the types and amounts of salt-formingcations. For example, by increasing the level of divalent cations (e.g.,Ca, Mg) and elevating the pH of aqueous dispersions of the polymersabove pH 1, the resultant polymer salts are especially useful as filmsand coatings.

1. Type B Repeat Units

Type B repeat units in accordance with the invention are dicarboxylaterepeat units derived from monomers of maleic acid and/or anhydride,fumaric acid and/or anhydride, mesaconic acid and/or anhydride,substituted maleic acid and/or anhydride, substituted fumaric acidand/or anhydride, substituted mesaconic acid and/or anhydride, mixturesof the foregoing, and any isomers, esters, acid chlorides, and partialor complete salts of any of the foregoing. As used herein with respectto the type B repeat units, “substituted” species refers to alkylsubstituents (preferably C1-C6 straight or branched chain alkyl groupssubstantially free of ring structures), and halo substituents (i.e., nomore than about 5 mole percent of either ring structures or halosubstituents, preferably no more than about 1 mole percent of either);the substituents are normally bound to one of the carbons of acarbon-carbon double bond of the monomer(s) employed. Similarly, the“salts” of the type B repeat units refers to partial or complete saltsprepared using salt-forming cations selected from the group consistingof metals, amines, and mixtures thereof. In preferred forms, the totalamount of type B repeat units in the polymers of the invention shouldrange from about 1-70 mole percent, more preferably from about 20-65mole percent, and most preferably from about 35-55 mole percent, wherethe total amount of all of the repeat units in the polymer is taken as100 mole percent.

Maleic acid, methylmaleic acid, maleic anhydride, methylmaleicanhydride, and mesaconic acid (either alone or as various mixtures) arethe most preferred monomers for generation of type B repeat units. Thoseskilled in the art will appreciate the usefulness of in situ conversionof acid anhydrides to acids in a reaction vessel just before or evenduring a reaction. However, it is also understood that whencorresponding esters (e.g., maleic or citraconic esters) are used asmonomers during the initial polymerization, this should be followed byhydrolysis (acid or base) of pendant ester groups to generate a finalcarboxylated polymer substantially free of ester groups.

2. Type C Repeat Units

Type C repeat units in accordance with the invention are derived frommonomers of itaconic acid and/or anhydride, substituted itaconic acidand/or anhydride, as well as isomers, esters, acid chlorides, andpartial or complete salts of any of the foregoing. The type C repeatunits are present in the preferred polymers of the invention at a levelof from about 1-80 mole percent, more preferably from about 15-75 molepercent, and most preferably from about 20-55 mole percent, where thetotal amount of all of the repeat units in the polymer is taken as 100mole percent.

The itaconic acid monomer used to form type C repeat unit has onecarboxyl group, which is not directly attached to the unsaturatedcarbon-carbon double bond used in the polymerization of the monomer.Hence, the preferred type C repeat unit has one carboxyl group directlybound to the polymer backbone, and another carboxyl group spaced by acarbon atom from the polymer backbone. The definitions and discussionrelating to “substituted,” “salt,” and useful salt-forming cations(metals, amines, and mixtures thereof) with respect to the type C repeatunits, are the same as those set forth for the type B repeat units.

Unsubstituted itaconic acid and itaconic anhydride, either alone or invarious mixtures, are the most preferred monomers for generation of typeC repeat units. Again, if itaconic anhydride is used as a startingmonomer, it is normally useful to convert the itaconic anhydride monomerto the acid form in a reaction vessel just before or even during thepolymerization reaction. Any remaining ester groups in the polymer arenormally hydrolyzed, so that the final carboxylated polymer issubstantially free of ester groups.

3. Type G Repeat Units

Type G repeat units in accordance with the invention are derived fromsubstituted or unsubstituted sulfonate-bearing monomers possessing atleast one carbon-carbon double bond and at least one sulfonate group, inacid, partial or complete salt, or other form, and which aresubstantially free of aromatic rings and amide groups (i.e., no morethan about 5 mole percent of either aromatic rings or amide groups,preferably no more than about 1 mole percent of either). The type Grepeat units are preferably selected from the group consisting of C1-C8straight or branched chain alkenyl sulfonates, substituted formsthereof, and any isomers or salts of any of the foregoing; especiallypreferred are alkenyl sulfonates selected from the group consisting ofvinyl, allyl, and methallylsulfonic acids or salts. The total amount oftype G repeat units in the polymers of the invention should range fromabout 0.1-65 mole percent, more preferably from about 1-35 mole percent,and most preferably from about 1-25 mole percent, where the total amountof all of the repeat units in the polymer is taken as 100 mole percent.The definitions and discussion relating to “substituted,” “salt,” anduseful salt-forming cations (metals, amines, and mixtures thereof) withrespect to the type G repeat units, are the same as those set forth forthe type B repeat units.

Vinylsulfonic acid, allylsulfonic acid, and methallylsulfonic acid,either alone or in various mixtures, are deemed to be the most preferredmonomers for generation of type G repeat units. It has also been foundthat alkali metal salts of these acids are also highly useful asmonomers. In this connection, it was unexpectedly discovered that duringpolymerization reactions yielding the novel polymers of the invention,the presence of mixtures of alkali metal salts of these monomers withacid forms thereof does not inhibit completion of the polymerizationreaction. By the same token, mixtures of monomers of maleic acid,itaconic acid, sodium allyl sulfonate, and sodium methallyl sulfonate donot inhibit the polymerization reaction.

Further Preferred Characteristics of the Novels Polymers

As noted previously, the total abundance of type B, C, and G repeatunits in the polymers of the invention is preferably at least about 90mole percent, more preferably at least about 96 mole percent, and mostpreferably the polymers consist essentially of or are 100 mole percentB, C, and G-type repeat units. It will be understood that the relativeamounts and identities of polymer repeat units can be varied, dependingupon the specific properties desired in the resultant polymers.Moreover, it is preferred that the polymers of the invention contain nomore than about 10 mole percent (more preferably no more than about 5mole percent) of any of (I) non-carboxylate olefin repeat units, (ii)ether repeat units, (iii) ester repeat units, (iv) non-sulfonatedmonocarboxylic repeat units, and (v) amide-containing repeat units.“Non-carboxylate” and “non-sulfonated” refers to repeat units havingessentially no carboxylate groups or sulfonate groups in thecorresponding repeat units. Advantageously, the mole ratio of the type Band type C repeat units in combination to the type G repeat units (thatis, the mole ratio of (B+C)/G) should be from about 0.5-20:1, morepreferably from about 2:1-20:1, and still more preferably from about2.5:1-10:1. Still further, the polymers should be essentially free(e.g., less than about 1 mole percent) of alkyloxylates or alkyleneoxide (e.g., ethylene oxide)-containing repeat units, and most desirablyentirely free thereof.

The preferred polymers of the invention have the repeat units thereofrandomly located along the polymer chain without any ordered sequence ofrepeat units. Thus, the polymers hereof are not, e.g., alternating withdifferent repeat units in a defined sequence along the polymer chain.

It has also been determined that the preferred polymers of the inventionshould have a very high percentage of the repeat units thereof bearingat least one anionic group, e.g., at least about 80 mole percent, morepreferably at least about 90 mole percent, still more preferably atleast about 95 mole percent, and most preferably essentially all of therepeat units contain at least one anionic group. It will be appreciatedthat the B and C repeat units have two anionic groups per repeat unit,whereas the preferred sulfonate repeat units have one anionic group perrepeat unit.

For a variety of applications, certain tetrapolymer compositions arepreferred, i.e., a preferred polymer backbone composition range (by molepercent, using the parent monomer names of the corresponding repeatunits) is: maleic acid 35-50%; itaconic acid 20-55%; methallylsulfonicacid 1-25%; and allylsulfonic sulfonic acid 1-20%, where the totalamount of all of the repeat units in the polymer is taken as 100 molepercent. It has also been found that even small amounts of repeat units,which are neither B nor C repeat units, can significantly impact theproperties of the final polymers, as compared with prior BC polymers.Thus, even 1 mole percent of each of 2 different G repeat units canresult in a tetrapolymer exhibiting drastically different behaviors, ascompared with BC polymers.

The molecular weight of the polymers is also highly variable, againdepending principally upon the desired properties. Generally, themolecular weight distribution for polymers in accordance with theinvention is conveniently measured by size exclusion chromatography.Broadly, the molecular weight of the polymers ranges from about800-50,000, and more preferably from about 1000-5000. For someapplications, it is advantageous that at least 90% of the finishedpolymer be at or above a molecular weight of about 1000 measured by sizeexclusion chromatography in 0.1 M sodium nitrate solution via refractiveindex detection at 35° C. using polyethylene glycol standards. Ofcourse, other techniques for such measurement can also be employed.

The polymers of the invention may be mixed with or complexed with metalor non-metal ions, and especially those selected from the group ofsimple cations such as the amines, alkali metals, Fe, Mn, Mg, Zn, Cu,Ni, Co, Mo, V, Cr, Si, B, Ca, and compounds containing these cations,e.g., boric acid, borates, molybdates, more complex cations such asvanadyl ions [VO]²⁺, and other complex ions containing vanadium, andmixtures of any of the foregoing.

The polymers of the invention can also be used in formulationscontaining a wide variety of other ingredients, including but notlimited to alcohols, diols, polyols, organic acids, polyvinyl alcohols,dyes, plastics, and mixtures thereof.

Syntheses of the Polymers of the Invention

Virtually any conventional method of free radical polymerization may besuitable for the synthesis of the polymers of the invention. However, apreferred and novel synthesis may be used, which is applicable not onlyfor the production of the polymers of the invention, but also for thesynthesis of polymers containing dicarboxylate repeat units andsulfonate repeat units and preferably containing at least onecarbon-carbon double bond. Such types of polymers are disclosed in U.S.Pat. Nos. 5,536,311 and 5,210,163.

Generally speaking, the new synthesis methods comprise carrying out afree radical polymerization reaction between dicarboxylate and sulfonaterepeat units in the presence of hydrogen peroxide andvanadium-containing species to achieve a conversion to polymer in excessof 90%, and more preferably in excess of 98%, by mole. That is, adispersion of the dicarboxylate and sulfonated monomers is created andfree radical initiator(s) are added followed by allowing the monomers topolymerize.

Of course, the preferred dicarboxylate and sulfonate repeat units arethose described previously as B, C, and G repeat units. Moreover, it hasbeen found that acceptable polymers can be synthesized having relativelylow amounts of maleic-type B repeat units, without creating excessunreacted monomers. U.S. Pat. No. 5,135,677 describes synthesis ofpolymers containing maleic acid and other water soluble repeat units.The '677 patent teaches that the amount of maleic repeat units is atleast 50 weight percent, more preferably at least 75 weight percent, andthat if smaller amounts of maleic repeat units are employed, largeamounts of residual monomers are created and the resultant polymers arepoor in biodegradability. However, it has been found that by judiciousselection of the B, C, and G repeat units of the invention, essentiallycomplete polymerization is achieved even with maleic-type B repeat unitsbelow 50 mole percent of the reaction mixture, as noted previously.

Preferably, hydrogen peroxide is the sole initiator used in thereaction, but in any case, it is advantageous to conduct the reaction inthe absence of any substantial quantities of other initiators (i.e., thetotal weight of the initiator molecules used should be about 95% byweight hydrogen peroxide, more preferably about 98% by weight, and mostpreferably 100% by weight thereof). Various sources of vanadium may beemployed, with vanadium oxysulfates being preferred.

It has been discovered that it is most advantageous to perform thesepolymerization reactions in substantially aqueous dispersions (e.g., thedispersants are at least about 95% by weight water, more preferably atleast about 98% by weight water, and most preferably 100% by weightwater). The aqueous dispersions may also contain additional monomer(s),but only to the minor extent noted.

It has also been found that the preferred polymerization reactions maybe carried out without the use of inert atmospheres, e.g., in an ambientair environment. As is well known in the art, free radicalpolymerization reactions in dispersions are normally conducted in a waythat excludes the significant presence of oxygen. As a result, theseprior techniques involve such necessary and laborious steps asdegassing, inert gas blanketing of reactor contents, monomer treatmentsto prevent air from being present, and the like. These prior expedientsadd to the cost and complexity of the polymerizations, and can presentsafety hazards. However, in the polymerizations of the polymers of thepresent invention, no inert gas or other related steps are required,although they may be employed if desired.

One preferred embodiment comprises creating highly concentrated aqueousdispersions of solid monomer particles (including saturated dispersionscontaining undissolved monomers) at a temperature of from about 50-125°C., more preferably from about 75-110° C., and adding vanadiumoxysulfate to give a vanadium concentration in the dispersion of fromabout 1-1000 ppm, and more preferably from about 5-500 ppm (metalsbasis). This is followed by the addition of hydrogen peroxide over aperiod of from about 30 minutes-24 hours (more preferably from about 1-5hours) in an amount effective to achieve polymerization. This process iscommonly carried out in a stirred tank reactor equipped with facilitiesfor controlling temperature and composition, but any suitable equipmentused for polymerization may be employed.

Another highly preferred and efficient embodiment involves charging astirred tank reactor with water, followed by heating and the addition ofmonomers to give a dispersion having from about 40-75% w/w solidsconcentration. Where maleic and/or itaconic monomers are employed, theymay be derived either from the corresponding acid monomers, or from insitu conversion of the anhydrides to acid in the water. Carboxylate andsulfonated monomers are preferred in their acid and/or anhydride form,although salts may be used as well. Surprisingly, it has been found thatincomplete monomer dissolution is not severely detrimental to thepolymerization; indeed, the initially undissolved fraction of monomerswill dissolve at some time after polymerization has been initiated.

After the initial heating and introduction of monomers, the reactorcontents are maintained at a temperature between about 80-125° C., withthe subsequent addition of vanadium oxysulfate. Up to this point in thereaction protocol, the order of addition of materials is not critical.After introduction of vanadium oxysulfate, a hydrogen peroxide solutionis added over time until substantially all of the monomers are convertedto polymer. Peroxide addition may be done at a constant rate, a variablerate, and with or without pauses, at a fixed or variable temperature.The concentration of peroxide solution used is not highly critical,although the concentration on the low end should not dilute the reactorcontents to the point where the reaction becomes excessively slow orimpractically diluted. On the high end, the concentration should notcause difficulties in performing the polymerization safely in theequipment being used.

After the polymerization is completed, the cations present may be leftas they are, or additional cations may be added. For example, thereactor contents may be neutralized to a higher pH by the addition ofvarious alkali metal or alkaline earth metal cations, ammonia, amines,or any other suitable cation source, thereby providing various mixedsalts of the polymer, if desired.

Preferably, the polymerization reactions of the invention are carriedout to exclude substantial amounts of dissolved iron species (i.e., morethan about 5% by weight of such species, and more preferablysubstantially less, on the order of below about 5 ppm, and mostadvantageously under about 1 ppm). This is distinct from certain priortechniques requiring the presence of iron-containing materials.Nonetheless, it is acceptable to carry out the polymerization of theinvention in 304 or 316 stainless steel reactors. It is also preferredto exclude from the polymerization reaction any significant amounts (normore than about 5% by weight) of the sulfate salts of ammonium, amine,alkali and alkaline earth metals, as well as their precursors andrelated sulfur-containing salts, such as bisulfites, sulfites, andmetabisulfites. It has been found that use of these sulfate-relatedcompounds leaves a relatively high amount of sulfates and the like inthe final polymers, which either must be separated or left as a productcontaminant.

The high polymerization efficiencies of the preferred syntheses resultfrom the use of water as a solvent and without the need for othersolvents, elimination of other initiators (e.g., azo, hydroperoxide,persulfate, organic peroxides) iron and sulfate ingredients, the lack ofrecycling loops, so that substantially all of the monomers are convertedto the finished polymers in a single reactor. This is further augmentedby the fact that the polymers are formed first, and subsequently, ifdesired, partial or complete salts can be created. The important factorsare the simultaneous presence of water solvent, peroxide initiator,vanadium compound, and monomers provided at appropriate times and atuseful temperatures. This can be arranged in any equipment and in anyfashion known in the art, i.e., the manor in which this is arranged isnot critical. For example, a certain proportion of the monomers may bein water solution in a reaction vessel, while additional monomers andperoxide are added to the vessel as the reaction proceeds in thepresence of appropriate vanadium compound levels.

EXAMPLES

The following Examples 1-4 describe preferred synthesis techniques forpreparing polymers; it should be understood, however, that theseExamples are provided by way of illustration only and nothing thereinshould be taken as a limitation on the overall scope of the invention.

Example 1 Exemplary Synthesis

Apparatus:

A cylindrical reactor was used, capable of being heated and cooled, andequipped with efficient mechanical stirrer, condenser, gas outlet (opento atmosphere), solids charging port, liquids charging port, thermometerand peroxide feeding tube.

Procedure: Water was charged into the reactor, stirring was initiatedalong with heating to a target temperature of 95° C. During this phase,itaconic acid, sodium methallylsulfonate, sodium allylsulfonate, andmaleic anhydride were added so as to make a 50% w/w solids dispersionwith the following monomer mole fractions:

-   -   maleic: 45%    -   itaconic: 35%    -   methallylsulfonate: 15%    -   allylsulfonate: 5%        When the reactor temperature reached 95° C., vanadium oxysulfate        was added to give a vanadium metal concentration of 25 ppm by        weight. After the vanadium salt fully dissolved, hydrogen        peroxide (as 50% w/w dispersion) was added continuously over 3        hours, using the feeding tube. The total amount of hydrogen        peroxide added was 5% of the dispersion weight in the reactor        prior to peroxide addition. After the peroxide addition was        complete, the reactor was held at 95° C. for two hours, followed        by cooling to room temperature.

The resulting polymer dispersion was found to have less than 2% w/wtotal of residual monomers as determined by chromatographic analysis.

Example 2 Exemplary Synthesis

Apparatus:

Same as Example 1

Procedure: Water was charged into the reactor, stirring was initiatedalong with heating to a target temperature of 100° C. During this phase,itaconic acid, sodium methallylsulfonate, sodium allylsulfonate, andmaleic anhydride were added so as to make a 70% w/w solids dispersionwith the following monomer mole fractions:

-   -   maleic: 45%    -   itaconic: 50%    -   methallylsulfonate: 4%    -   allylsulfonate: 1%        When the reactor temperature reached 100° C., vanadium        oxysulfate was added to give a vanadium metal concentration of        25 ppm by weight. After the vanadium salt fully dissolved,        hydrogen peroxide (as 50% w/w dispersion) was added continuously        over 3 hours, using the feeding tube. The total amount of        hydrogen peroxide added was 7.5% of the dispersion weight in the        reactor prior to peroxide addition. After the peroxide addition        was complete, the reactor was held at 100° C. for two hours,        followed by cooling to room temperature.

The resulting polymer dispersion was found to have less than 1% w/wtotal of residual monomers as determined by chromatographic analysis.

Example 3 Exemplary Synthesis

A terpolymer salt dispersion containing 70% by weight polymer solids inwater was prepared using a cylindrical reactor capable of being heatedand cooled, and equipped with an efficient mechanical stirrer, acondenser, a gas outlet open to the atmosphere, respective ports forcharging liquids and solids to the reactor, a thermometer, and aperoxide feeding tube.

Water (300 g) was charged into the reactor with stirring and heating toa target temperature of 95° C. During heating, itaconic acid, sodiummethallylsulfonate, and maleic anhydride were added so as to make a 75%w/w solids dispersion with the following monomer mole fractions: maleicanhydride—20%; itaconic acid—60%; methallylsulfonate sodium salt—20%.When the monomers were initially added, they were in suspension in thewater. As the temperature rose, the monomers became more fully dissolvedbefore polymerization was initiated, and the maleic anhydride washydrolyzed to maleic acid. When the reactor temperature reached 95° C.,vanadium oxysulfate was added to yield a vanadium metal concentration of50 ppm by weight of the reactor contents at the time of addition of thevanadium salt. After the vanadium salt fully dissolved, hydrogenperoxide was added as a 50% w/w dispersion in water continuously overtwo hours. At the time of hydrogen peroxide addition, not all of themonomers were completely dissolved, achieving what is sometimes referredto as “slush polymerization”; the initially undissolved monomers weresubsequently dissolved during the course of the reaction. The totalamount of hydrogen peroxide added equaled 5% of the dispersion weight inthe reactor before addition of the peroxide.

After the peroxide addition was completed, the reaction mixture was heldat 95° C. for two hours, and then allowed to cool to room temperature.The resulting polymer dispersion had a pH of slightly below 1.0 and wasa partial sodium salt owing to the sodium cation on the sulfonatemonomers. The dispersion was found to have a monomer content of lessthan 2% w/w, calculated as a fraction of the total solids in thereaction mixture, as determined by chromatographic analysis.Accordingly, over 98% w/w of the initially added monomers were convertedto polymer.

Example 4 Preparation of Tetrapolymer Partial Salts

A tetrapolymer partial sodium salt dispersion containing 40% by weightpolymer solids in water was prepared by the preferred free radicalpolymerization synthesis of the invention, using an aqueous monomerreaction mixture having 45 mole percent maleic anhydride, 35 molepercent itaconic acid, 15 mole percent methallylsulfonate sodium salt,and 5 mole percent allylsulfonate. The final tetrapolymer dispersion hada pH of slightly below 1.0 and was a partial sodium salt owing to thesodium cation on the sulfonate monomers. At least about 90% of themonomers were polymerized in the reaction.

This sodium partial salt tetrapolymer was used to create a series of 40%solids in water partial salts. In each instance, apart from the sodiumpresent in the tetrapolymer mixture, appropriate bases or baseprecursors (e.g., carbonates), or mixtures thereof were added to theaqueous tetrapolymer at room temperature to generate the correspondingsalts. In all instances save for Salt A below, the in situ sodiumresulting from the synthesis was the primary source of sodium used inthe conversions; in Salt A, the bulk of the sodium came from the use ofNaOH. Specifically, the following basic reactants were employed withquantities of the tetrapolymer to give the following salts:

-   -   Salt A—sodium hydroxide, pH 7.    -   Salt B—ammonium hydroxide and a minor amount of sodium        hydroxide, pH 2.    -   Salt C—calcium carbonate and a minor amount of sodium hydroxide,        pH 1.5.    -   Salt D—calcium carbonate and a minor amount of sodium hydroxide,        pH 3.5.    -   Salt E—isopropylamine, pH 4.8.    -   Salt F—triethanolamine, pH 7.    -   Salt G—zinc carbonate, manganese carbonate, cupric basic        carbonate, and sodium hydroxide, pH 6 (Zn content 2% by weight,        Mn content 1% by weight, Cu content 250 ppm).    -   Salt H—zinc carbonate, pH 3 (Zn content 5% by weight).    -   Salt I—manganese carbonate, pH 4 (Mn content 5% by weight).        Mixtures of the Novel Polymers of the Invention with Other        Polymers

The novel polymers hereof may be a part of polymer mixtures orfractions, which include other types of polymers, especiallydicarboxylate polymers, and particularly those containing maleic anditaconic repeat units. These mixed polymer formulations may be used inall of the contexts hereafter described.

Preferred types of different polymers useful in the mixed polymerproducts are referred to as “Class IA” and “Class II” polymers.

Class IA Polymers

Class IA polymers contain both carboxylate and sulfonate functionalgroups, but are not the tetra- and higher order polymers of Class I. Forexample, terpolymers of maleic, itaconic, and allylsulfonic repeatunits, which are per se known in the prior art, will function as thepolyanionic polymer component of the compositions of the invention. TheClass IA polymers thus are normally homopolymers, copolymers, andterpolymers, advantageously including repeat units individually andindependently selected from the group consisting of type B, type C, andtype G repeat units, without the need for any additional repeat units.Such polymers can be synthesized in any known fashion, and can also beproduced using the previously described Class I polymer synthesis.

Class IA polymers preferably have the same molecular weight ranges andthe other specific parameters (e.g., pH and polymer solids loading)previously described in connection with the Class I polymers, and may beconverted to partial or complete salts using the same techniquesdescribed with reference to the Class I polymers. Class IA polymers aremost advantageously synthesized using the techniques described above inconnection with the Class I polymers.

Class II Polymers

Broadly speaking, the polyanionic polymers of this class are of the typedisclosed in U.S. Pat. No. 8,043,995, which incorporated by referenceherein in its entirety. The polymers include repeat units derived fromat least two different monomers individually and respectively taken fromthe group consisting of what have been denominated for ease of referenceas B′ and C′ monomers; alternately, the polymers may be formed ashomopolymers or copolymers from recurring C′ monomers. The repeat unitsmay be randomly distributed throughout the polymer chains.

In detail repeat unit B′ is of the general formula

and repeat unit C′ is of the general formula

wherein each R₇ is individually and respectively selected from the groupconsisting of H, OH, C₁-C₃₀ straight, branched chain and cyclic alkyl oraryl groups, C₁-C₃₀ straight, branched chain and cyclic alkyl or arylformate (C₀), acetate (C₁), propionate (C₂), butyrate (C₃), etc. up toC₃₀ based ester groups, R′CO₂ groups, OR′ groups and COOX groups,wherein R′ is selected from the group consisting of C₁-C₃₀ straight,branched chain and cyclic alkyl or aryl groups and X is selected fromthe group consisting of H, the alkali metals, NH₄ and the C₁-C₄ alkylammonium groups, R₃ and R₄ are individually and respectively selectedfrom the group consisting of H, C₁-C₃₀ straight, branched chain andcyclic alkyl or aryl groups, R₅, R₆, R₁₀ and R₁₁ are individually andrespectively selected from the group consisting of H, the alkali metals,NH₄ and the C₁-C₄ alkyl ammonium groups, Y is selected from the groupconsisting of Fe, Mn, Mg, Zn, Cu, Ni, Co, Mo, V, W, the alkali metals,the alkaline earth metals, polyatomic cations containing any of theforegoing (e.g., VO⁺²), amines, and mixtures thereof; and R₈ and R₉ areindividually and respectively selected from the group consisting ofnothing (i.e., the groups are non-existent), CH₂, C₂H₄, and C₃H₆.

As can be appreciated, the Class II polymers typically have differenttypes and sequences of repeat units. For example, a Class II polymercomprising B′ and C′ repeat units may include all three forms of B′repeat units and all three forms of C′ repeat units. However, forreasons of cost and ease of synthesis, the most useful Class II polymersare made up of B′ and C′ repeat units. In the case of the Class IIpolymers made up principally of B′ and C′ repeat units, R₅, R₆, R₁₀, andR₁₁ are individually and respectively selected from the group consistingof H, the alkali metals, NH₄, and the C₁-C₄ alkyl ammonium groups. Thisparticular Class II polymer is sometimes referred to as a butanedioicmethylenesuccinic acid copolymer and can include various salts andderivatives thereof.

The Class II polymers may have a wide range of repeat unitconcentrations in the polymer. For example, Class II polymers havingvarying ratios of B′:C′ (e.g., 10:90, 60:40, 50:50 and even 0:100) arecontemplated and embraced by the present invention. Such polymers wouldbe produced by varying monomer amounts in the reaction mixture fromwhich the final product is eventually produced and the B′ and C′ typerepeat units may be arranged in the polymer backbone in random order orin an alternating pattern.

The Class II polymers may have a wide variety of molecular weights,ranging for example from 500-5,000,000, depending chiefly upon thedesired end use. Additionally, n can range from about 1-10,000 and morepreferably from about 1-5,000.

Preferred Class II polymers are usually synthesized using dicarboxylicacid monomers, as well as precursors and derivatives thereof. Forexample, polymers containing mono and dicarboxylic acid repeat unitswith vinyl ester repeat units and vinyl alcohol repeat units arecontemplated; however, polymers principally comprised of dicarboxylicacid repeat units are preferred (e.g., at least about 85%, and morepreferably at least about 93%, of the repeat units are of thischaracter). Class II polymers may be readily complexed with salt-formingcations using conventional methods and reactants.

Synthesis of the Class II Polymers

In general, the Class II polymers are made by free radicalpolymerization serving to convert selected monomers into the desiredpolymers with repeat units. Such polymers may be further modified toimpart particular structures and/or properties. A variety of techniquescan be used for generating free radicals, such as addition of peroxides,hydroperoxides, azo initiators, persulfates, percarbonates, per-acid,charge transfer complexes, irradiation (e.g., UV, electron beam, X-ray,gamma-radiation and other ionizing radiation types), and combinations ofthese techniques. Of course, an extensive variety of methods andtechniques are well known in the art of polymer chemistry for initiatingfree-radical polymerizations. Those enumerated herein are but some ofthe more frequently used methods and techniques. Any suitable techniquefor performing free-radical polymerization is likely to be useful forthe purposes of practicing the present invention.

The polymerization reactions are carried out in a compatible solventsystem, namely a system which does not unduly interfere with the desiredpolymerization, using essentially any desired monomer concentrations. Anumber of suitable aqueous or non-aqueous solvent systems can beemployed, such as ketones, alcohols, esters, ethers, aromatic solvents,water and mixtures thereof. Water alone and the lower (C₁-C₄) ketonesand alcohols are especially preferred, and these may be mixed with waterif desired. In some instances, the polymerization reactions are carriedout with the substantial exclusion of oxygen, and most usually under aninert gas such as nitrogen or argon. There is no particular criticalityin the type of equipment used in the synthesis of the polymers, i.e.,stirred tank reactors, continuous stirred tank reactors, plug flowreactors, tube reactors and any combination of the foregoing arranged inseries may be employed. A wide range of suitable reaction arrangementsare well known to the art of polymerization.

In general, the initial polymerization step is carried out at atemperature of from about 0° C. to about 120° C. (more preferably fromabout 30° C. to about 95° C. for a period of from about 0.25 hours toabout 24 hours and even more preferably from about 0.25 hours to about 5hours). Usually, the reaction is carried out with continuous stirring.

After the polymerization reaction is complete, the Class II polymers maybe converted to partial or saturated salts using conventional techniquesand reactants.

Preferred Class II Maleic-Itaconic Polymers

The most preferred Class II polymers are composed of maleic and itaconicB′ and C′ repeat units and have the generalized formula

where X is either H or another salt-forming cation, depending upon thelevel of salt formation.

In a specific example of the synthesis of a maleic-itaconic Class IIpolymer, acetone (803 g), maleic anhydride (140 g), itaconic acid (185g) and benzoyl peroxide (11 g) were stirred together under inert gas ina reactor. The reactor provided included a suitably sized cylindricaljacketed glass reactor with mechanical agitator, a contents temperaturemeasurement device in contact with the contents of the reactor, an inertgas inlet, and a removable reflux condenser. This mixture was heated bycirculating heated oil in the reactor jacket and stirred vigorously atan internal temperature of about 65−70° C. This reaction was carried outover a period of about 5 hours. At this point, the contents of thereaction vessel were poured into 300 g water with vigorous mixing. Thisgave a clear solution. The solution was subjected to distillation atreduced pressure to drive off excess solvent and water. After sufficientsolvent and water have been removed, the solid product of the reactionprecipitates from the concentrated solution, and is recovered. Thesolids are subsequently dried in vacuo. A schematic representation ofthis reaction is shown below.

Step 1

Step 2

Preferred Uses of the Novel Polymers of the Invention

The novel (Class I) polymers of the invention, either alone, as a partof a mixed polymer product, and/or with other ingredients, can be usedin a variety of contexts, some of which are described below. All of theprevious disclosures relating to the Class I, IA, and II polymers isapplicable to each of the uses described below, i.e., the entirety ofthe previous polymer disclosures should be considered as incorporated byreference into each of the following categories of use. Likewise, anydefinitions set forth in the categories of use are to be considered asapplicable to all such categories.

1. Agricultural Actives

The Class I polymers hereof (with or without complexed ions) may be useddirectly as agricultural actives. For example, such polymers may bedispersed in a liquid aqueous medium and applied foliarly to plantleaves or applied to the earth adjacent growing plants. It has beenfound that the polymers increase the plant's uptake of bothpolymer-borne metal nutrients and ambient non-polymer nutrients found inadjacent soil. In such uses, effective amounts of compositionscomprising the above-defined polymers are employed, either in liquiddispersions or in dried, granular form. Thus, application of polymeralone results in improved plant growth characteristics, presumably byincreasing the availability of naturally occurring ambient nutrients.Typically, the polymers are applied at a level of from about 0.001 toabout 100 lbs. polymer per acre of soil or growing plants, and morepreferably from about 0.005 to about 50 lbs. polymer per acre, and stillmore preferably from about 0.01 to about 2 lbs.

2. Fertilizer Uses

In other preferred uses, the Class I polymers may be used to formcomposite products where the polymers are in intimate contact withfertilizer products including but not limited to phosphate-basedfertilizers such as MAP, DAP, triple superphosphate, ordinarysuperphosphate, any one of a number of well known N-P-K fertilizerproducts, and/or fertilizers containing nitrogen materials such asammonia (anhydrous or aqueous), ammonium nitrate, ammonium sulfate,urea, ammonium phosphates, sodium nitrate, calcium nitrate, potassiumnitrate, nitrate of soda, urea formaldehyde, metal (e.g., zinc, iron)ammonium phosphates; phosphorous materials such as calcium phosphates(normal phosphate and super phosphate), ammonium phosphate, ammoniatedsuper phosphate, phosphoric acid, superphosphoric acid, basic slag, rockphosphate, colloidal phosphate, bone phosphate; potassium materials suchas potassium chloride, potassium sulfate, potassium nitrate, potassiumphosphate, potassium hydroxide, potassium carbonate; calcium materials,such as calcium sulfate, calcium carbonate, calcium nitrate; magnesiummaterials, such as magnesium carbonate, magnesium oxide, magnesiumsulfate, magnesium hydroxide; sulfur materials such as ammonium sulfate,sulfates of other fertilizers discussed herein, ammonium thiosulfate,elemental sulfur (either alone or included with or coated on otherfertilizers); micronutrients such as Zn, Mn, Cu, Fe, B, Mo, and othermicronutrients discussed herein; oxides, sulfates, chlorides, andchelates of such micronutrients (e.g., zinc oxide, zinc sulfate and zincchloride); such chelates sequestered onto other carriers such as EDTA;boron materials such as boric acid, sodium borate or calcium borate;organic wastes and waste waters such as manure, sewage, food processingindustry by-products, and pulp and paper mill by-products; andmolybdenum materials such as sodium molybdate. As known in the art,these fertilizer products can exist as dry powders/granules or as waterdispersions. The fertilizers may be of the conventional variety, or theymay be starter fertilizers.

In such contexts, the Class I polymers may be mixed with the fertilizerproducts, applied as a surface coating to the fertilizer products, orotherwise thoroughly mixed with the fertilizer products. Preferably, insuch combined fertilizer/polymer compositions, the fertilizer is in theform of particles having an average diameter of from about powder size(less than about 0.001 cm) to about 10 mm, more preferably from about0.1 mm to about 5 mm, and still more preferably from about 0.15 mm toabout 3 mm. The polymer is present in such combined products at a levelof from about 0.01 g to about 7 g polymer per 100 g fertilizer (e.g.,phosphate-based fertilizer), more preferably from about 0.08 g to about5 g polymer per 100 g fertilizer, and still more preferably from about0.09 g to about 2 g polymer per 100 g fertilizer. Again, the polymericfraction of such combined products may include the polymers definedabove, or such polymers complexed with the aforementioned ions. In thecase of the combined fertilizer/polymer products, the combined productis applied at a level so that the amount of polymer applied is fromabout 10-150 g polymer per acre of soil, more preferably from about30-125 g polymer per acre, and still more preferably from about 40-120 gpolymer per acre of soil. The combined products can likewise be appliedas liquid dispersions or as dry granulated products, at the discretionof the user. When polymers in accordance with the present invention areused as a coating, the polymer comprises between about 0.005% and about15% by weight of the coated fertilizer product, more preferably thepolymer comprises between about 0.01% and about 10% by weight of thecoated fertilizer product, and most preferably between 0.5% and about 1%by weight of the coated fertilizer product. It has been found thatpolymer-coated fertilizer products obtain highly desirablecharacteristics due to the alteration of mechanical and physicalproperties of the fertilizer.

Especially preferred Class I polymers for use in agricultural contextsare synthesized as partial sodium salts and include the following repeatunits: maleic—from about 20-55 mole percent, more preferably from about25-50 mole percent, and most preferably from about 30-45 mole percent;itaconic—from about 35-65 mole percent, more preferably from about 40-60mole percent, and most preferably about 50 mole percent; totalsulfonated—from about 2-40 mole percent, more preferably from about 3-25mole percent, and most preferably from about 5-20 mole percent. Thetotal sulfonated fraction is preferably made up of a combination ofmethallylsulfonic and allylsulfonic repeat units, namely,methallylsulfonic—from about 1-20 mole percent, more preferably fromabout 3-15 mole percent, and most preferably from about 4-6 molepercent, and allylsulfonic—from about 0.1-10 mole percent, morepreferably from about 0.5-8 mole percent, and most preferably from about1-5 mole percent. These types of polymers are typically converted topartial or complete salts (preferably using cations such as alkalimetal, ammonium, zinc, and mixtures thereof) at a pH of from about0.2-4, more preferably from about 0.3-3, and most preferably from about1-2.5.

As mentioned, these preferred agricultural-use Class I polymers areadvantageously initially synthesized as partial sodium salts. This isdue to the fact that the most preferred sulfonated repeat units arederived from the sodium salts, for reasons of cost and availability.

One preferred polymer of this type is a partial sodium salt having a pHof about 1, with a repeat unit molar composition of maleic 45 molepercent, itaconic 50 mole percent, methallylsulfonic 4 mole percent, andallylsulfonic 1 mole percent. This specific polymer is referred toherein as the “T5” polymer.

Useful variants of the T5 polymer include mixed sodium and zinc partialsalts having about 5% w/w Zn on a metals basis and with a pH of about 3.It is made by reacting the T5 tetrapolymer with basic zinc carbonate inwater. Alternately, the product may be made by reaction with zinc metal.

Another type of preferred polymer is a “T-20” tetrapolymer containingabout 30 mole percent maleic repeat units, about 50 mole percentitaconic repeat units, and a total of about 20 mole percent sulfonatedrepeat units, made up of about 15 mole percent methallylsulfonate repeatunits and about 5 mole percent allylsulfonate repeat units. Variants ofT-20 tetrapolymers include partial salts (preferably alkali metal,ammonium, zinc, and mixtures thereof) having a pH of from about 1-3. Onesuch variant is a partial mix sodium and ammonium salt at a pH of about2.5, made by adding ammonia to the partial T-20 sodium salt aqueoussolution until the target pH is achieved. This polymer has a significantlipophyllic character and is useful in pesticide-containingformulations.

Preferred formulations for coating granular nitrogenous fertilizers(e.g., urea) include a novel tetrapolymer of the invention (preferablyT5 polymer), boric acid, low molecular weight polyvinyl alcohol, andwater. For example, such coating formulations may have from about 20-50%w/w (most preferably about 34% w/w) tetrapolymer, from about 0.1-5% w/w(more preferably about 1.5% w/w) low molecular weight polyvinyl alcohol,and from about 25-60% w/w (most preferably about 57.5% w/w) water. Suchformulations are compatible with colorant dyes and provide superiorcoating performance.

Preferred formulations for addition to liquid nitrogenous fertilizersinclude a novel tetrapolymer of the invention in the form of a mixedcalcium/sodium salt (preferably T5 polymer), lactic acid, boric acid,and water at a pH of from about 0.5-3. For example, such formulationsmay have from about 20-50% w/w (most preferably about 35.5% w/w)tetrapolymer, from about 20-40% w/w (more preferably about 30% w/w)lactic acid, from about 2-10% w/w (more preferably about 4.5% w/w) andfrom about 20-45% w/w (most preferably about 30% w/w) water.

Example 5 Evaluation of Tetrapolymer Partial Salt as a PhosphorusFertilizer Enhancer

The above-described ammonium/sodium tetrapolymer Salt B was tested todetermine its ability to prevent fixation of phosphorus in dispersions.In soils, the fixing of phosphorus (phosphates) with cations, such asCa, Mn, Mg, Al, and Fe, limit phosphorus uptake by plants, which in turndepresses yields. This soil interaction can be simulated in water usingwater-soluble phosphates (P2O5) in dispersion. These dispersions createan ideal environment for fixation testing, with visible precipitation ofphosphates being determined.

A first stock dispersion of 1000 ppm free calcium ion made from calciumchloride was prepared and aliquots thereof were pipetted into eightseparate 50 mL Erlenmeyer flasks, followed by dilution with deionizedwater to 50 mL of total volume. This yielded two sets of flasks nos. 1and 2, each set having four individual flasks respectively containing10, 100, 500, and 1000 ppm of free calcium ion in water.

A second stock dispersion of 1000 ppm free iron ion made from ferroussulfate was also created and pipetted into eight additional Erlenmeyerflasks to create two sets of flasks nos. 3 and 4, each set having fourindividual flasks respectively containing 10, 100, 500, and 1000 ppm offree iron ion in water.

The B tetrapolymer partial salt (a sodium/ammonium salt, pH about 2.5)was added to the flasks of sets 1 and 3 at a rate of 0.50% (v/v) torepresent a typical liquid fertilizer usage rate. Sets 2 and 4 were leftuntreated as controls. A 1% by weight phosphate dispersion was madeusing standard 10-34-0 liquid phosphate fertilizer, and this waspipetted into all 16 of the Erlenmeyer flasks in a stepwise fraction,using 0.5 mL aliquots, up to a total of 5.0 mL phosphate dispersion. Theextent of phosphate precipitation was recorded after each aliquot wasadded to the flasks, using a percentage scale where 0% was clear andcolorless, and 100% was a solid opaque precipitate (lower concentrationsof cations did not reach 100% and were completely bonded at a level ofabout 75% precipitate). The results of these tests are set forth in thefollowing Tables 1 and 2.

TABLE 1 Example 5, Ca Flasks, Sets 1 and 2 Phosphate Addition - mL CaReaction Flasks 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 10 ppm 0% 0% 0%0% 0% 0% 0% 0% 0% 0% 10 ppm w/Polymer 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 100ppm 0% 30%  60%  75%  75%  75%  75%  75%  75%  75%  100 ppm w/Polymer 0%0% 0% 0% 0% 0% 0% 0% 0% 0% 500 ppm 10%  40%  70%  100%  100%  100% 100%  100%  100%  100%  500 ppm w/Polymer 0% 0% 0% 0% 0% 20%  30%  50% 100%  100%  1000 ppm 30%  60%  100%  100%  100%  100%  100%  100%  100% 100%  1000 ppm w/Polymer 0% 0% 0% 0% 20%  40%  70%  100%  100%  100% 

TABLE 2 Example 5, Fe Flasks, Sets 3 and 4 Phosphate Addition - mL FeReaction Flasks 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 10 ppm 0% 0% 0%0% 0% 0% 0% 0% 0% 0% 10 ppm w/Polymer 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 100ppm 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 100 ppm w/Polymer 0% 0% 0% 0% 0% 0% 0%0% 0% 0% 500 ppm 40%  80%  100%  100%  100%  100%  100%  100%  100% 100%  500 ppm w/Polymer 0% 0% 0% 0% 0% 0% 25%  50%  100%  100%  1000 ppm70%  100%  100%  100%  100%  100%  100%  100%  100%  100%  1000 ppmw/Polymer 0% 0% 0% 0% 0% 20%  40%  80%  100%  100% 

As is evident from the foregoing data, the polymers of the inventionsignificantly reduced precipitation in all of the Ca and Fe reactionflasks, save for the 10 ppm dispersions, which had no precipitation atany level of phosphate addition. In the Ca reaction flasks at 100 ppm,the polymer-supplemented flasks exhibited no precipitation at any levelof phosphate addition, whereas the 100 ppm flask with no polymerexhibited significant precipitation (corresponding to prevention ofphosphorus fixation) beginning at the 1.5 mL level. Similarly, in the Fereaction flasks at 500 and 1000 ppm phosphate addition levels, theperformance of the polymer-supplemented flasks was significantly betterthan the no-polymer flasks.

3. Uses with Sulfur-Bearing Compounds

One particularly important agricultural utility of the novel Class Ipolymers of the invention is the ability of the polymers to enhance theagricultural effectiveness of sulfur-bearing compounds such as gypsum,one or more members of the Kieserite Group, potassium magnesium sulfate,elemental sulfur, and mixtures thereof. The polymers may be applied assurface coatings as solid fertilizers, or may be added to solutionizedliquid fertilizers as a liquid; this combined liquid material may thenbe sprayed on soils prior to planting. Moreover, the polymers liberatesoluble calcium and soluble sulfur-containing species from gypsum andother minerals in compositions containing significant amounts of calciumsulfate. Calcium sulfate exists in a wide range of forms, crystalstructures, hydration levels, and particle morphologies, but the calciumsulfate content thereof has been difficult to exploit for plantnutrition purposes, owing to the poor solubility of the calcium andsulfur-containing species therein.

It has been found that the addition of comparatively small levels of thenovel polymers of the invention applied to solid calcium sulfate orcalcium sulfate-containing materials serves to increase the liberationof calcium and soluble sulfur species from calcium sulfate or similarmaterials. Generally, the polymers are used at a level of from about0.01-10% w/w, more preferably from about 0.05-2% w/w, where the totalweight of the polymer/calcium sulfate or calcium sulfate-containingproducts is taken as 100% by weight.

Example 6 Class I Tetrapolymer Treatment of Gypsum

In this test, granulated gypsum was coated with the T5 polymer, whichwas diluted with water to give a polymer content of about 40% w/w. Thispolymeric material was applied to the gypsum at a rate of 0.50% w/w.

Three no-polymer gypsum controls were run for each test, along withthree gypsum polymer-added replications. In each test, a 1 g sample ofthe uncoated or coated gypsum was placed in a 50 mL Erlenmeyer flask,followed by the addition of 10 mL of water and shaking on areciprocating shaker at low setting for a selected period of time. Afterthe selected shaking period, the content of each flask was filtered intoa 50 mL centrifuge tube through Whatman 1 filter paper. Thereupon, thepH of the filtered solution was measured and the solution was thendiluted 10 times with 2.0% nitric acid and analyzed via inductivelycoupled plasma Optical Emission Spectroscopy (ICP-OES) for sulfur andcalcium content. The pH of the filtered solution was also recorded. Theresults are set forth in the following tables.

TABLE 1 Example 6 20 min. shake % Ca % S pH % Ca mean % S mean ControlSamples 1.55 1.69 6.96 1.81 2.04 Rep. 2 2.17 2.43 6.7 Rep. 3 1.72 2.006.58 T5 Polymer Samples 1.41 1.54 5.99 1.86 2.11 Rep. 2 1.96 2.26 6.14Rep. 3 2.20 2.53 6.17

TABLE 2 Example 6 60 min. shake % Ca % S pH % Ca mean % S mean ControlSamples 1.71 1.91 7.08 1.74 1.98 Rep. 2 1.72 1.99 7.13 Rep. 3 1.78 2.067.25 T5 Polymer Samples 1.46 1.61 6.00 1.87 2.12 Rep. 2 1.86 2.12 6.05Rep. 3 2.31 2.64 6.48

TABLE 3 Example 6 240 min. shake % Ca % S pH % Ca mean % S mean ControlSamples 1.72 1.93 6.94 1.81 2.10 Rep. 2 1.93 2.24 7.32 Rep. 3 1.77 2.127.23 T5 Polymer Samples 1.52 1.69 6.32 2.09 2.35 Rep. 2 1.99 2.20 6.45Rep. 3 2.76 3.17 6.35

TABLE 4 Example 6 24 hr. shake % Ca % S pH % Ca mean % S mean ControlSamples 1.88 2.14 7.24 1.82 2.10 Rep. 2 1.84 2.10 7.21 Rep. 3 1.73 2.077.24 T5 Polymer Samples 2.00 2.19 6.79 2.10 2.35 Rep. 2 1.96 2.23 6.95Rep. 3 2.36 2.62 6.53As can be seen, as the shake time increased, the amount of free sulfurand calcium increased significantly over the controls, confirming thatthe T5 polymer gypsum coating increased the amount of available sulfurfor plant uptake.

Still further increased availability of sulfur and calcium can beobtained using a coating mixture comprising 35% w/w T5 tetrapolymer,about 2% w/w low molecular weight polyvinyl alcohol, and about 40% w/wglycolic acid, with the balance being water. By removing most of thewater and adding glycolic acid and PVA, improved coating behaviors werenoted, allowing smaller quantities of polymer to be used.

4. Uses with Liquid or Solutionized Fertilizers

Use of alpha-hydroxy carboxylic acid compounds with the polymers of theinvention in the context of liquid or solutionized fertilizers can yieldimproved results. The alpha-hydroxiy acids may be used singly or inmixtures of 2 or more acids. The most useful alpha-hydroxy acids aresaturated and essentially free of double bonds and carbon ringstructures, including both aliphatic and aromatic ring structures (i.e.,no more than about 5 mole percent of double bonds or ring structures).Such alpha-hydroxy acids possess at least one carboxylic acid functionalgroup and have at least one hydroxyl group on the carbon atom adjacentto the carboxylate group. Especially preferred acids of this characterinclude lactic acid (D, L, or racemic mixtures are useful), glycolicacid, citric acid, tartaric acid, tartronic acid, glyceric acid, anddihydroxypropanedioic acid. The alpha-hydroxy acids may have more thanone carboxylic acid functional group per molecule, more than onealphahydroxyl group, or any combination thereof.

The preferred polymer/alpha-hydroxy acid formulations generally includefrom about 10-45% w/w, more preferably from about 15-35% w/w, of thepolymers of the invention, which preferably includes at least one ClassI polymer; from about 3-60% w/w, more preferably from about 10-40% w/w,of alpha-hydroxy carboxylic acid(s); and the balance being an inertsolvent, preferably water. The foregoing ranges are based upon the totalweight of the formulations taken as 100% by weight. The followingrepresentative formulation has been found to be particularly useful foruse with liquid or solutionized fertilizers, especially solutionizedgypsum: 35% w/w of the previously described T5 polymer, 30% w/w ofglycolic acid, and with the balance being water.

The polymer/alpha-hydroxy carboxylic acid formulations may be furtherimproved with the addition of polyvinyl alcohols (PVA's) thereto. Whileessentially all PVA's are useful, preferred PVA's are of relatively lowaverage molecular weight, such that a 4% w/w solution of the PVA's inwater at 20° C. ranges between about 1-1000 centipoise. Very smallamounts of PVA's may be used in a range of from about 0.1% w/w-10% w/wof the total composition, and more preferably from about 0.05% w/w-2%w/w. It is also possible to use more than one molecular weight of PVA,but the PVA combinations advantageously are within the above viscosityranges. Still further, preferred PVA's have high levels of hydrolysis,where at least 97 mole percent, and preferably at least about 98 molepercent, of the functional groups are hydrolyzed. A representativecomposition for use with gypsum includes 35% w/w of the T5 polymer, 30%w/w of glycolic acid, 1.5% w/w PVA (e.g., DuPont Elvanol 70-03), and thebalance being water.

The pH levels of the liquid or solutionized fertilizers including thealpha-hydroxy acid formulations should be from about 0.5-3, morepreferably about 1.

Example 7 Addition of Class I Tetrapolymer to UAN

In this series of tests, standard UAN was supplemented with 0.50% byweight of a mixture containing 35.5% by weight partial calcium salt ofthe T5 polymer (pH about 1.0), 4.5% by weight boric acid, 30% by weightlactic acid, with the balance being water. This material was used at alevel of 40 gal/acre corresponding to 120 lbs of nitrogen/acre withdifferent types of planted hybrid corn seeds. Comparative tests werealso performed using no-polymer UAN, and UAN supplemented with therecommended label amount of commercially available NutriSphere-N forliquid fertilizers. All of the tests were done in 6 replications withthe liquid fertilizers broadcast applied before emergence, two daysafter planting. Corn yields were recorded for each test and averaged.

TABLE 1 Example 7 UAN Treatment Hybrid Yield (Bu/acre) None CL2133 106.2+NutriSphere-N 121.6 +T5 mixture 148.6 None INT9333 115.8 +NutriSphere-N137.6 +T5 mixture 140.6 None P8210HR 124.1 +NutriSphere-N 129 +T5mixture 139.8 None DK30-23 91.9 +NutriSphere-N 93.9 +T5 mixture 139.7

5. Specific Uses with Potassium-Containing Granular Fertilizers

Another significant agricultural utility of the Class I polymers of theinvention involves use with potassium-containing granular fertilizers inorder to decrease fertilizer losses. That is, the polymers may beapplied directly to at least partially water soluble granular potassiumfertilizer, and especially potassium chloride-based fertilizers, at alevel of from about 0.001-10% by weight, more preferably from about0.004-2% by weight, based upon the total weight of the polymer/potassiumfertilizer material taken as 100% by weight. In order to form suitablecoatings on these fertilizers without generation of significant amountsof hydrochloric acid, it is generally preferred that the polymers beneutralized with a suitable cation to a pH of from about 0.1-4, and morepreferably about 1. One preferred formulation involves creating apartial salt of the T5 polymer (at a concentration of 50% w/w) inaqueous dispersion at 20° C. by reacting the polymer with 45% w/wpotassium hydroxide to reach a pH of about 0.1-4. The resultingdispersion is adjusted by evaporation and water addition to give a 40%w/w solids dispersion at room temperature. This composition, referred toas “T5-K-Na,” is coated onto commercial potassium chloride granules at alevel of from about 0.001% w/w-5% w/w.

It has been found that use of the novel polymers of the invention is notessential in formulations including soluble potassium-containing solids.Thus, this aspect of the invention contemplates provision offormulations comprising a mixture of a Class I and/or Class II polymer(having at least about 10%, more preferably at least about 25%, of thefunctional groups thereon being anionic) in partial or complete saltform, with substantially all of the cations therein being alkaline metaland at a pH between about 0.5-3, and more preferably about 1. Suchformulations are applied to at least partially solublepotassium-containing solids and allowed to dry, so that the driedresidue thereof is applied to the surface of the solids. The same levelsof use described above with reference to the calcium sulfate productsare applicable to these potassium products as well. The polymer isusually present at a level of from about 0.001-10% by weight, morepreferably from about 0.004-2% by weight, based upon the total weight ofthe polymer/potassium-containing solids product taken as 100% by weight.

6. Uses as Seed Coatings

Another alternative use of the Class I polymers in accordance with thepresent invention includes using the polymers as seed coatings. In suchcases, the polymers comprise at least about 0.001-10% by weight of thecoated seed, more preferably from about 0.004-2% by weight of the coatedseed. Use of the polymer as a seed coating provides polymer in closeproximity to the seed when planted so that the polymer can exert itsbeneficial effects in the environment where it is most needed. That is,the new polymers provide an environment conducive to enhanced plantgrowth in the area where the effects can be localized around the desiredplant. In the case of seeds, the polymer coating provides an enhancedopportunity for seed germination, subsequent plant growth, and anincrease in plant nutrient availability, which is provided by thepolymer salts.

In preferred practice, the Class I polymers are in aqueous dispersionand have a relatively high metals content, and particularlymicronutrient metals, such as Zn, Mn, B, Fe, Mo, and Cu, to providesufficient micronutrients for optimum seed growth. Moreover, thepolymers are desirably solutions relatively free of suspended or settledsolids for reasons of homogeneity and cosmetic appearance, and shouldhave a pH in the range of from about 2-8, and preferably from about 5-7.In practice, the polymers are applied to the surfaces of seeds in anyconvenient fashion, and allowed to dry thereon, so that the finishedseeds have the dried residue of the original liquid polymer andnutrients on the surfaces thereof.

7. Uses in Reducing Atmospheric Ammonia

The novel Class I polymers hereof may be used to treat livestock orpoultry confinement facilities in order to reduce and mitigate theeffects of gaseous ammonia within the facility. Generally, suchfacilities have a manure collection zone, upright walls forming anenclosure, and a roof substantially covering the zone. This utilityinvolves applying a treatment material to the manure within thecollection zone in an amount effective to lower the concentration ofgaseous ammonia within the facility. Such material comprises an aqueousmixture of a polymer in accordance with the present invention, andparticularly an amine, alkali metal or alkaline earth (e.g., calcium orammonium) partial or saturated salt of the polymer. Preferably, thetreating mixture is applied directly into the collection zone (e.g.,manure pit) below the enclosure. The treating material including thepolymer hereof should be applied at a level of from about 0.005-3gallons per ton of manure, and more preferably from about 0.01-2.5gallons per ton. The composition is preferably acidic having a pH offrom about 1-5, and more preferably from about 2-4. The treatingmaterial is operable to reduce the amount of gaseous ammonia within theconfinement zone within 24 hours after application of the materials.

U.S. Patent Publication 2014/0041431 is incorporated by reference hereinin its entirety. This publication describes techniques for reducingatmospheric ammonia through use of Class II polymers. These sametechniques without alteration can be used with the Class I polymers ofthis invention, and also all different mixtures of Class I, Class IA,and Class II polymers.

It is sometimes useful to employ a plurality of different polymers inthe treating compositions. For example, useful compositions may includefrom about 40-80% (more preferably 55-75%) by weight of a partialcalcium salt of a Class I polymer of the invention, and from about20-60% (more preferably 25-45%) by weight of a partial ammonium salt ofthe same or different polymer in accordance with the invention. Both ofthese polymers are in the form of 40% w/w aqueous dispersions, so thatthe total amount of polymer per se in each is 40% of the above-recitedranges

The polymers of the invention (i.e., Class I polymers, or differentmixtures of Class I, Class IA, and Class II polymers) may also be used,alone or in combination with other polymers, to treat areas subject toammonia gas evolution, e.g., household pet litters, in order to reducethe ammonia odor emanating therefrom.

The complete treatment materials should preferably contain at leastabout 30-60% by weight (more preferably from about 35-50% by weight)polymer solids derived from all of the polymers present in the treatmentmaterials, and from about 40-70% by weight (more preferably from about50-65% by weight) water. Other ingredients may be used apart from thepolymers and water, such as pH adjustment agents, buffering agents,preservatives, and emulsifiers. Any such other ingredients arepreferably used at a minor level, e.g., from about 1-10% by weight. ThepH of the complete treating materials should be acidic, preferably fromabout 1-5, more preferably from about 2-4.

When the preferred treating materials comprise calcium and ammoniumpartial salts of the polymers, it is desirable that the amount of thecalcium partial salt polymer is greater than the amount of the ammoniumpartial salt polymer, on a weight basis. That is, taking the totalweight of both polymer salt solids as 100% by weight, the calciumpartial salt copolymer solids should be present at a level of from about50-80% by weight (more preferably from about 55-75% by weight, and mostpreferably from about 60-65% by weight), and the ammonium partial saltcopolymer solids should be present at a level of from about 20-50% byweight (more preferably from about 25-45% by weight, and most preferablyfrom about 35-40% by weight).

Application of the dual partial salt copolymer materials of theinvention is quite straightforward. In the case of manure collectionpits, the material need only be poured onto the top of the manure andwill quite readily spread and diffuse throughout the mass of the manureto promptly reduce the amount of gaseous nitrogen generated andmaintained within the confinement facility. In the case of dairy orpoultry barns having floor structures with litter and manure atop ormixed with the litter, the treating material is advantageously sprayedonto the top of the litter-manure mixture, with or without mixing. Hereagain, the action of the treating material is quite prompt andlong-lasting.

Generally, the treating mixtures are used at a level of from about0.005-3 gallons of the material per ton of manure, more preferably fromabout 0.01-2.5 gallons/ton, still more preferably from about 0.02-1gallon per ton, and most preferably from about 0.03-0.035 gallon perton.

Almost immediately upon application of the treating material to themanure, the amount of gaseous ammonia within the confinement facility isperceptibly lowered, and such reduction persists for a considerabletime. Generally, the prevailing amount of gaseous ammonia should bereduced by at least about 50% (more preferably at least about 60%)within 24 hours after application. A single treatment also preferablyserves to maintain at least about a 30% gaseous ammonia reduction (morepreferably at least about 40%) for at least about 14 days (morepreferably at least about 21 days).

8. Uses as Animal Feed and/or Water Amendments

U.S. patent application Ser. No. 14/049,887, filed Oct. 9, 2013,discloses the use of Class I and/or Class II polymers as animal feed orwater amendments serving to lower ammonia concentrations in the animal'sexcrement. That application is incorporated by reference herein in itsentirety. The methods, animal feeds, and animal waters disclosed thereincan be directly duplicated, without any alternations, in the context ofthe present invention save for the use of any mixture of Class I, ClassIA, and Class II polymers hereof. Thus, the types of polymer salts, therange of polymer solids, and the amounts of water remain the same in thepresent invention. Likewise, the same specific methods of use may beemployed in the context of the present invention, with the onlydifference being the particular polymers utilized.

For example, conventional poultry feeds comprising feed ingredientsincluding quantities of corn and soybean meal can be improved using theamendments containing Class I polymers alone or in combination withother polymers, such as the Class IA and Class II polymers. In likemanner, poultry water may be supplemented in the same fashion. In eitherinstance, the amount of amendment used should be sufficient to reducevolatilized ammonia derived from the feces of poultry, as compared withpoultry receiving the same feed and/or water, but without theamendments. Similarly, mammalian animal feeds and waters can be improvedby the addition of the copolymers of the invention, again in amountssufficient to reduce volatilized ammonia derived from mammalianexcrement, as compared with animals receiving the same feed and/orwater, but without the amendments.

The complete amendments should preferably contain at least about 30-60%by weight of total copolymer solids (more preferably from about 35-50%by weight solids), and from about 40-70% by weight water (mostpreferably from about 50-65% water). However, the amendments may alsoinclude other ingredients apart from the two partial salt copolymers andwater, such as pH adjustment agents, buffering agents, preservatives,and emulsifiers. Any such other ingredients are preferably used at aminor level, e.g., from about 1-10% by weight. The pH of the completeamendments should be acid, preferably from about 1-5, more preferablyfrom about 2-4.

A preferred amendment comprises an aqueous mixture including a partialcalcium salt of a Class I copolymer and a partial ammonium salt of aClass I copolymer, the calcium partial salt copolymer solids should bepresent in an amount greater than the amount of the ammonium partialsalt copolymer solids therein. That is, taking the total weight of bothcopolymer salt solids as 100% by weight, the calcium partial saltcopolymer solids should be present at a level of from about 50-80% byweight (more preferably from about 55-75% by weight, and most preferablyfrom about 60-65% by weight), and the ammonium partial salt copolymersolids should be present at a level of from about 20-50% by weight (morepreferably from about 25-45% by weight, and most preferably from about35-40% by weight). Also, the individual copolymer salts in water shouldboth have a pH on the order of from about 1-4.

Generally speaking, the amendments of the invention are administered toanimals by adding the amendments to otherwise conventional animal feeds,and/or adding the amendments to the animal water supply, or both.

In the case of poultry, use can be made of commercially available orcustom poultry feeds, which are typically substantially dry andparticulate in nature. Such feeds typically contain yellow corn at alevel of from about 45-65% by weight, together with soybean at a levelof from about 18-45% by weight. These feeds also commonly include avariety of other ingredients, such as meat and bone meals, fats, salt,limestone or oyster shell, amino acids, vitamins and minerals, and haveanalyses of protein (N×6.25) of from about 15-32%, and a MetabolizableEnergy (ME) value of from about 1100-1600 kcal/lb. Further informationabout conventional poultry feeds can be found in Poultry Nutrition andFeeding, Section 12, Animal Nutrition Handbook, pp. 316-331 (2009),which is wholly incorporated herein by reference. The amendments of theinvention, typically in aqueous liquid form, are sprayed or otherwiseapplied to the dry poultry feed ingredients with mixing, tosubstantially intersperse the copolymer materials with the feedingredients. The improved feed is then fed ad libitum to poultry. Thecomplete water/copolymer salt amendments should be present in animproved feed at a level of from about 0.05-0.25% by weight (morepreferably from about 0.1-0.2% by weight), where the total weight of thesupplemented or amended feed is taken as 100% by weight. Thiscorresponds to a level of from about 0.015-0.15% by weight (morepreferably 0.03-0.12% by weight) of copolymer solids per se in thepoultry feed.

In the case of adding the complete water/copolymer salt amendments topoultry water, the usage would typically be at a level of from about0.01-0.25% by volume, more preferably from about 0.05-0.2% by volume,where the total amount of supplemented or amended water is taken as 100%by volume. This corresponds to a level of from about 0.003-0.15% byvolume (more preferably 0.0045-0.12% by volume) of the copolymer solidsper se in the poultry water. Inasmuch as the preferred partial saltcopolymers of the invention and the MTM® product, are water soluble, thecomplete amendments readily mix and evenly disperse in the poultrywater.

The amendments of the invention, used either with poultry feed orpoultry water can be fed to virtually any poultry, e.g., chicken, duck,goose, peafowl, swan, ostrich, pigeon, turkey, guineafowl, pheasant,rhea, and emu.

Where the complete amendments are employed to supplement mammaliananimal feeds and/or waters, the same general techniques and amounts ofcomplete amendments and copolymers are employed. For example, theamendments may be directly mixed with animal feeds or used as a topdressing thereon. Likewise, the animals' water supply is supplemented asdescribed previously. The fact that the copolymers are water solublegreater facilitates uses thereof. The amendments of the invention may befed to a wide variety of livestock, e.g., mammals such as cattle, sheep,swine, and horses.

As indicated above, it is preferred that the amendments of the inventionbe used in the form of aqueous mixtures containing copolymer salt(s).However, and especially in the case of amendments to poultry or animalwaters, the copolymer solids can be added as is, and not in a completewater/copolymer amendment. In such instances, the above ranges ofaddition of the copolymers themselves are applicable.

9. Pesticide Adjuvants

The Class I polymers of the invention can be used to enhance theeffectiveness of a wide spectrum of pesticides. As used herein,“pesticide” refers to any agent with pesticidal activity (e.g.,herbicides, insecticides, fungicides, and nematocides) and is preferablyselected from the group consisting of insecticides, herbicides, andmixtures thereof, but normally excluding materials which assertedly havea plant-fertilizing effect, for example, sodium borate and zinccompounds such as zinc oxide, zinc sulfate, and zinc chloride. The wellknown pyrethroid and organophosphate pesticides are suitable for use inthe invention, as well as glyphosate and glufosinate herbicides.

In some cases, the polymer, which may be in the free acid, partial, orfull salt form, is in aqueous dispersion and has a pH of from about1-10, more preferably from about 2-7, and most preferably from 2-4, 7,and 8-9; the pH is often determined by the type of pesticide employed,inasmuch as some may be unstable in low pH ranges, while others breakdown at higher pH ranges. The polymers may be blended with the pesticideto form a mixture which then can be applied to soil, in foliarapplications, onto hard surfaces, as aerosols, as additives to liquid orsolid compositions (e.g., manure), or in any other context wherepesticidal activity is desired. Alternately, the pesticide and polymermay be simultaneously or sequentially (typically within 24 hours of eachother) applied to soil. Where mixed compositions are employed, they aretypically in the form of aqueous dispersions, generally having water,pesticide, and polymer fractions. Other minor ingredients may also beused in the compositions such as surfactants and pH adjustment agents,or any of the other aforementioned adjuvants or additives known in theart. Compositions comprising a polymer of the invention andmicronutrients have also proven to be very effective, withmicronutrients selected from the group consisting of Mn, Zn, Cu, Ni, Co,Mo, V, Cr, Fe, and B, with a combination of Mn, Zn, and Cu beingparticularly preferred. Micronutrient-supplemented polymers can be usedwith glyphosate, to avoid the characteristic blocking reactions betweenglyphosate and micronutrients.

The amount of polymer in the pesticide compositions of the invention canvary over wide limits, and the principal consideration is one of polymercost. Generally, the polymer should be present at a level of from about0.05-10% by weight (more preferably from about 0.1-4% by weight, andmost preferably from about 0.2-2% by weight) based upon the total weightof the pesticide composition taken as 100% by weight.

The pesticides used in the compositions of the invention are broadlyselected from insecticides and herbicides. In the context ofinsecticides, synthetic pyrethroids and organophosphates areparticularly preferred. For example, permethrin (C21H20Cl203,(3-phenoxyphenyl) methyl3-(2,2-dichloroethenyl)-2,2-dimethyl-cyclopropane-1-carboxylate,CAS#52645-53-1) and bifenthrin (C23H22ClF302,(2-methyl-3-phenylphenyl)methyl(1S,3S)-3-[(Z)-2-chloro-3,3,3-trifluoroprop-1-enyl]-2,2-dimethylcyclopropane-1-carboxylate,CAS#82657-04-3) are suitable pyrethroids. A typical organophosphatepesticide useful in the invention is malathion (C10H1906PS2,2-(dimethoxyphosphinothioylthio) butanedioic acid diethyl ester,CAS#121-75-5).

More generally, the following insecticides are useful in the invention:

-   antibiotic insecticides: allosamidin, thuringiensin    -   macrocyclic lactone insecticides        -   avermectin insecticides: abamectin, doramectin, emamectin,            eprinomectin, ivermectin, selamectin        -   milbemycin insecticides: lepimectin, ilbemectin, milbemycin            oxime, moxidectin        -   spinosyn insecticides: spinetoram, spinosad-   arsenical insecticides: calcium arsenate, copper acetoarsenite,    copper arsenate, lead arsenate, potassium arsenite, sodium arsenite-   botanical insecticides: anabasine, azadirachtin, d-limonene,    nicotine, pyrethrins (cinerins (cinerin I, cinerin II), jasmolin I,    jasmolin II, pyrethrin I, pyrethrin II), quassia, rotenone, ryania,    sabadilla-   carbamate insecticides: bendiocarb, carbaryl    -   benzofuranyl methylcarbamate insecticides: benfuracarb,        carbofuran, carbosulfan, decarbofuran, furathiocarb    -   dimethylcarbamate insecticides: dimetan, dimetilan, hyquincarb,        pirimicarb    -   oxime carbamate insecticides: alanycarb, aldicarb, aldoxycarb,        butocarboxim, butoxycarboxim, methomyl, nitrilacarb, oxamyl,        tazimcarb, thiocarboxime, thiodicarb, thiofanox    -   phenyl methylcarbamate insecticides: allyxycarb, aminocarb,        bufencarb, butacarb, carbanolate, cloethocarb, dicresyl,        dioxacarb, EMPC, ethiofencarb, fenethacarb, fenobucarb,        isoprocarb, methiocarb, metolcarb, mexacarbate, promacyl,        promecarb, propoxur, trimethacarb, XMC, xylylcarb-   desiccant insecticides: boric acid, diatomaceous earth, silica gel-   diamide insecticides: chlorantraniliprole, cyantraniliprole,    flubendiamide-   dinitrophenol insecticides: dinex, dinoprop, dinosam, DNOC-   fluorine insecticides: barium hexafluorosilicate, cryolite, sodium    fluoride, sodium hexafluorosilicate, sulfluramid-   formamidine insecticides: amitraz, chlordimeform, formetanate,    formparanate-   fumigant insecticides: acrylonitrile, carbon disulfide, carbon    tetrachloride, chloroform, chloropicrin, para-dichlorobenzene,    1,2-dichloropropane, ethyl formate, ethylene dibromide, ethylene    dichloride, ethylene oxide, hydrogen cyanide, iodomethane, methyl    bromide, methylchloroform, methylene chloride, naphthalene,    phosphine, sulfuryl fluoride, tetrachloroethane-   inorganic insecticides: borax, boric acid, calcium polysulfide,    copper oleate, diatomaceous earth, mercurous chloride, potassium    thiocyanate, silica gel, sodium thiocyanate, see also arsenical    insecticides, see also fluorine insecticides-   insect growth regulators    -   chitin synthesis inhibitors: bistrifluron, buprofezin,        chlorfluazuron, cyromazine, diflubenzuron, flucycloxuron,        flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron,        penfluron, teflubenzuron, triflumuron    -   juvenile hormone mimics: epofenonane, fenoxycarb, hydroprene,        kinoprene, methoprene, pyriproxyfen, triprene    -   juvenile hormones: juvenile hormone I, juvenile hormone II,        juvenile hormone III    -   moulting hormone agonists: chromafenozide, halofenozide,        methoxyfenozide, tebufenozide    -   moulting hormones: a-ecdysone, ecdysterone    -   moulting inhibitors: diofenolan    -   precocenes: precocene I, precocene II, precocene III    -   unclassified insect growth regulators: dicyclanil-   nereistoxin analogue insecticides: bensultap, cartap, thiocyclam,    thiosultap-   nicotinoid insecticides: flonicamid    -   nitroguanidine insecticides: clothianidin, dinotefuran,        imidacloprid, thiamethoxam    -   nitromethylene insecticides: nitenpyram, nithiazine    -   pyridylmethylamine insecticides: acetamiprid, imidacloprid,        nitenpyram, thiacloprid-   organochlorine insecticides: bromo-DDT, camphechlor, DDT (pp′-DDT),    ethyl-DDD, HCH (gamma-HCH, lindane), methoxychlor,    pentachlorophenol, TDE    -   cyclodiene insecticides: aldrin, bromocyclen, chlorbicyclen,        chlordane, chlordecone, dieldrin, dilor, endosulfan        (alpha-endosulfan), endrin, HEOD, heptachlor, HHDN, isobenzan,        isodrin, kelevan, mirex-   organophosphorus insecticides    -   organophosphate insecticides: bromfenvinfos, chlorfenvinphos,        crotoxyphos, dichlorvos, dicrotophos, dimethylvinphos,        fospirate, heptenophos, methocrotophos, mevinphos,        monocrotophos, naled, naftalofos, phosphamidon, propaphos, TEPP,        tetrachlorvinphos    -   organothiophosphate insecticides: dioxabenzofos, fosmethilan,        phenthoate        -   aliphatic organothiophosphate insecticides: acethion,            amiton, cadusafos, chlorethoxyfos, chlormephos, demephion            (demephion-O, demephion-S), demeton (demeton-O, demeton-S),            demeton-methyl (demeton-O-methyl, demeton-S-methyl),            demeton-S-methylsulphon, disulfoton, ethion, ethoprophos,            IPSP, isothioate, malathion, methacrifos, oxydemeton-methyl,            oxydeprofos, oxydisulfoton, phorate, sulfotep, terbufos,            thiometon            -   aliphatic amide organothiophosphate insecticides:                amidithion, cyanthoate, dimethoate, ethoate-methyl,                formothion, mecarbam, omethoate, prothoate, sophamide,                vamidothion            -   oxime organothiophosphate insecticides: chlorphoxim,                phoxim, phoxim-methyl        -   heterocyclic organothiophosphate insecticides: azamethiphos,            coumaphos, coumithoate, dioxathion, endothion, menazon,            morphothion, phosalone, pyraclofos, pyridaphenthion,            quinothion            -   benzothiopyran organothiophosphate insecticides:                dithicrofos, thicrofos            -   benzotriazine organothiophosphate insecticides:                azinphos-ethyl, azinphos-methyl            -   isoindole organothiophosphate insecticides: dialifos,                phosmet            -   isoxazole organothiophosphate insecticides: isoxathion,                zolaprofos            -   pyrazolopyrimidine organothiophosphate insecticides:                chlorprazophos, pyrazophos            -   pyridine organothiophosphate insecticides: chlorpyrifos,                chlorpyrifos-methyl            -   pyrimidine organothiophosphate insecticides:                butathiofos, diazinon, etrimfos, lirimfos,                pirimiphos-ethyl, pirimiphos-methyl, primidophos,                pyrimitate, tebupirimfos            -   quinoxaline organothiophosphate insecticides:                quinalphos, quinalphos-methyl            -   thiadiazole organothiophosphate insecticides:                athidathion, lythidathion, methidathion, prothidathion            -   triazole organothiophosphate insecticides: isazofos,                triazophos        -   phenyl organothiophosphate insecticides: azothoate,            bromophos, bromophos-ethyl, carbophenothion, chlorthiophos,            cyanophos, cythioate, dicapthon, dichlofenthion, etaphos,            famphur, fenchlorphos, fenitrothion, fensulfothion,            fenthion, fenthion-ethyl, heterophos, jodfenphos,            mesulfenfos, parathion, parathion-methyl, phenkapton,            phosnichlor, profenofos, prothiofos, sulprofos, temephos,            trichlormetaphos-3, trifenofos    -   phosphonate insecticides: butonate, trichlorfon    -   phosphonothioate insecticides: mecarphon        -   phenyl ethylphosphonothioate insecticides: fonofos,            trichloronat        -   phenyl phenylphosphonothioate insecticides: cyanofenphos,            EPN, leptophos    -   phosphoramidate insecticides: crufomate, fenamiphos, fosthietan,        mephosfolan, phosfolan, pirimetaphos    -   phosphoramidothioate insecticides: acephate, isocarbophos,        isofenphos, isofenphos-methyl, methamidophos, propetamphos    -   phosphorodiamide insecticides: dimefox, mazidox, mipafox,        schradan-   oxadiazine insecticides: indoxacarb-   oxadiazolone insecticides: metoxadiazone-   phthalimide insecticides: dialifos, phosmet, tetramethrin-   pyrazole insecticides: chlorantraniliprole, cyantraniliprole,    dimetilan, tebufenpyrad, tolfenpyrad    -   phenylpyrazole insecticides: acetoprole, ethiprole, fipronil,        pyraclofos, pyrafluprole, pyriprole, vaniliprole-   pyrethroid insecticides-   pyrethroid ester insecticides: acrinathrin, allethrin    (bioallethrin), barthrin, bifenthrin, bioethanomethrin, cyclethrin,    cycloprothrin, cyfluthrin (beta-cyfluthrin), cyhalothrin,    (gamma-cyhalothrin, lambda-cyhalothrin), cypermethrin    (alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin,    zeta-cypermethrin), cyphenothrin, deltamethrin, dimefluthrin,    dimethrin, empenthrin, fenfluthrin, fenpirithrin, fenpropathrin,    fenvalerate (esfenvalerate), flucythrinate, fluvalinate    (tau-fluvalinate), furethrin, imiprothrin, metofluthrin, permethrin    (biopermethrin, transpermethrin), phenothrin, prallethrin,    profluthrin, pyresmethrin, resmethrin (bioresmethrin, cismethrin),    tefluthrin, terallethrin, tetramethrin, tralomethrin, transfluthrin-   pyrethroid ether insecticides: etofenprox, flufenprox, halfenprox,    protrifenbute, silafluofen-   pyrimidinamine insecticides: flufenerim, pyrimidifen-   pyrrole insecticides: chlorfenapyr-   tetramic acid insecticides: spirotetramat-   tetronic acid insecticides: spiromesifen-   thiazole insecticides: clothianidin, thiamethoxam-   thiazolidine insecticides: tazimcarb, thiacloprid-   thiourea insecticides: diafenthiuron-   urea insecticides: flucofuron, sulcofuron, see also chitin synthesis    inhibitors-   unclassified insecticides: closantel, copper naphthenate,    crotamiton, EXD, fenazaflor, fenoxacrim, hydramethylnon,    isoprothiolane, malonoben, metaflumizone, nifluridide, plifenate,    pyridaben, pyridalyl, pyrifluquinazon, rafoxanide, sulfoxaflor,    triarathene, triazamate.

The foregoing insecticides, and links for a further identification anddescription of the insecticides, can be found athttp://www.alanwood.net/pesticides/class_insecticides.html, which isincorporated herein in its entirety.

A particularly preferred herbicide is glyphosate (C3H8NO5P,[(phosphonomethyl)amino] acetic acid, CAS#1071-83-6). Other herbicideswhich can be used in the invention include:

-   amide herbicides: allidochlor, amicarbazone, beflubutamid, benzadox,    benzipram, bromobutide, cafenstrole, CDEA, cyprazole, dimethenamid    (dimethenamid-P), diphenamid, epronaz, etnipromid, fentrazamide,    flucarbazone, flupoxam, fomesafen, halosafen, isocarbamid, isoxaben,    napropamide, naptalam, pethoxamid, propyzamide, quinonamid,    saflufenacil, tebutam    -   anilide herbicides: chloranocryl, cisanilide, clomeprop,        cypromid, diflufenican, etobenzanid, fenasulam, flufenacet,        flufenican, ipfencarbazone, mefenacet, mefluidide, metamifop,        monalide, naproanilide, pentanochlor, picolinafen, propanil,        sulfentrazone arylalanine herbicides: benzoylprop, flamprop        (flamprop-M),        -   chloroacetanilide herbicides: acetochlor, alachlor,            butachlor, butenachlor, delachlor, diethatyl, dimethachlor,            metazachlor, metolachlor (S-metolachlor), pretilachlor,            propachlor, propisochlor, prynachlor, terbuchlor,            thenylchlor, xylachlor        -   sulfonanilide herbicides: benzofluor, cloransulam,            diclosulam, florasulam, flumetsulam, metosulam, perfluidone,            pyrimisulfan, profluazol    -   sulfonamide herbicides: asulam, carbasulam, fenasulam, oryzalin,        penoxsulam, pyroxsulam, see also sulfonylurea herbicides    -   thioamide herbicides: bencarbazone, chlorthiamid-   antibiotic herbicides: bilanafos-   aromatic acid herbicides:    -   benzoic acid herbicides: chloramben, dicamba, 2,3,6-TBA,        tricamba        -   pyrimidinyloxybenzoic acid herbicides: bispyribac,            pyriminobac        -   pyrimidinylthiobenzoic acid herbicides: pyrithiobac    -   phthalic acid herbicides: chlorthal    -   picolinic acid herbicides: aminopyralid, clopyralid, picloram    -   quinolinecarboxylic acid herbicides: quinclorac, quinmerac-   arsenical herbicides: cacodylic acid, CMA, DSMA, hexaflurate, MAA,    MAMA, MSMA, potassium arsenite, sodium arsenite-   benzoylcyclohexanedione herbicides: mesotrione, sulcotrione,    tefuryltrione, tembotrione-   benzofuranyl alkylsulfonate herbicides: benfuresate, ethofumesate-   benzothiazole herbicides: benazolin, benzthiazuron, fenthiaprop,    mefenacet, methabenzthiazuron-   carbamate herbicides: asulam, carboxazole, chlorprocarb,    dichlormate, fenasulam, karbutilate, terbucarb-   carbanilate herbicides: barban, BCPC, carbasulam, carbetamide, CEPC,    chlorbufam, chlorpropham, CPPC, desmedipham, phenisopham,    phenmedipham, phenmedipham-ethyl, propham, swep-   cyclohexene oxime herbicides: alloxydim, butroxydim, clethodim,    cloproxydim, cycloxydim, profoxydim, sethoxydim, tepraloxydim,    tralkoxydim-   cyclopropylisoxazole herbicides: isoxachlortole, isoxaflutole-   dicarboximide herbicides: cinidon-ethyl, flumezin, flumiclorac,    flumioxazin, flumipropyn, see also uracil herbicides-   dinitroaniline herbicides: benfluralin, butralin, dinitramine,    ethalfluralin, fluchloralin, isopropalin, methalpropalin, nitralin,    oryzalin, pendimethalin, prodiamine, profluralin, trifluralin-   dinitrophenol herbicides: dinofenate, dinoprop, dinosam, dinoseb,    dinoterb, DNOC, etinofen, medinoterb-   diphenyl ether herbicides: ethoxyfen    -   nitrophenyl ether herbicides: acifluorfen, aclonifen, bifenox,        chlomethoxyfen, chlornitrofen, etnipromid, fluorodifen,        fluoroglycofen, fluoronitrofen, fomesafen, furyloxyfen,        halosafen, lactofen, nitrofen, nitrofluorfen, oxyfluorfen-   dithiocarbamate herbicides: dazomet, metam-   halogenated aliphatic herbicides: alorac, chloropon, dalapon,    flupropanate, hexachloroacetone, iodomethane, methyl bromide,    monochloroacetic acid, SMA, TCA-   imidazolinone herbicides: imazamethabenz, imazamox, imazapic,    imazapyr, imazaquin, imazethapyr-   inorganic herbicides: ammonium sulfamate, borax, calcium chlorate,    copper sulfate, ferrous sulfate, potassium azide, potassium cyanate,    sodium azide, sodium chlorate, sulfuric acid-   nitrile herbicides: bromobonil, bromoxynil, chloroxynil,    dichlobenil, iodobonil, ioxynil, pyraclonil-   organophosphorus herbicides: amiprofos-methyl, anilofos, bensulide,    bilanafos, butamifos, 2,4-DEP, DMPA, EBEP, fosamine, glufosinate    (glufosinate-P), glyphosate, piperophos-   oxadiazolone herbicides: dimefuron, methazole, oxadiargyl, oxadiazon-   oxazole herbicides: carboxazole, fenoxasulfone, isouron, isoxaben,    isoxachlortole, isoxaflutole, monisouron, pyroxasulfone, topramezone-   phenoxy herbicides: bromofenoxim, clomeprop, 2,4-DEB, 2,4-DEP,    difenopenten, disul, erbon, etnipromid, fenteracol, trifopsime    -   phenoxyacetic herbicides: 4-CPA, 2,4-D, 3,4-DA, MCPA,        MCPA-thioethyl, 2,4,5-T    -   phenoxybutyric herbicides: 4-CPB, 2,4-DB, 3,4-DB, MCPB, 2,4,5-TB    -   phenoxypropionic herbicides: cloprop, 4-CPP, dichlorprop        (dichlorprop-P), 3,4-DP, fenoprop, mecoprop, (mecoprop-P)        -   aryloxyphenoxypropionic herbicides: chlorazifop, clodinafop,            clofop, cyhalofop, diclofop, fenoxaprop, (fenoxaprop-P),            fenthiaprop, fluazifop, (fluazifop-P), haloxyfop,            (haloxyfop-P), isoxapyrifop, metamifop, propaquizafop,            quizalofop, (quizalofop-P), trifop-   phenylenediamine herbicides: dinitramine, prodiamine-   pyrazole herbicides: azimsulfuron, difenzoquat, halosulfuron,    metazachlor, metazosulfuron, pyrazosulfuron, pyroxasulfone    -   benzoylpyrazole herbicides: benzofenap, pyrasulfotole,        pyrazolynate, pyrazoxyfen, topramezone    -   phenylpyrazole herbicides: fluazolate, nipyraclofen, pinoxaden,        pyraflufen-   pyridazine herbicides: credazine, pyridafol, pyridate-   pyridazinone herbicides: brompyrazon, chloridazon, dimidazon,    flufenpyr, metflurazon, norflurazon, oxapyrazon, pydanon-   pyridine herbicides: aminopyralid, cliodinate, clopyralid,    diflufenican, dithiopyr, flufenican, fluroxypyr, haloxydine,    picloram, picolinafen, pyriclor, pyroxsulam, thiazopyr, triclopyr-   pyrimidinediamine herbicides: iprymidam, tioclorim-   quaternary ammonium herbicides: cyperquat, diethamquat, difenzoquat,    diquat, morfamquat, paraquat-   thiocarbamate herbicides: butylate, cycloate, di-allate, EPTC,    esprocarb, ethiolate, isopolinate, methiobencarb, molinate,    orbencarb, pebulate, prosulfocarb, pyributicarb, sulfallate,    thiobencarb, tiocarbazil, tri-allate, vernolate-   thiocarbonate herbicides: dimexano, EXD, proxan-   thiourea herbicides: methiuron-   triazine herbicides: dipropetryn, indaziflam, triaziflam,    trihydroxytriazine    -   chlorotriazine herbicides: atrazine, chlorazine, cyanazine,        cyprazine, eglinazine, ipazine, mesoprazine, procyazine,        proglinazine, propazine, sebuthylazine, simazine,        terbuthylazine, trietazine    -   methoxytriazine herbicides: atraton, methometon, prometon,        secbumeton, simeton, terbumeton    -   methylthiotriazine herbicides: ametryn, aziprotryne, cyanatryn,        desmetryn, dimethametryn, methoprotryne, prometryn, simetryn,        terbutryn-   triazinone herbicides: ametridione, amibuzin, hexazinone,    isomethiozin, metamitron, metribuzin-   triazole herbicides: amitrole, cafenstrole, epronaz, flupoxam-   triazolone herbicides: amicarbazone, bencarbazone, carfentrazone,    flucarbazone, ipfencarbazone, propoxycarbazone, sulfentrazone,    thiencarbazone-   triazolopyrimidine herbicides: cloransulam, diclosulam, florasulam,    flumetsulam, metosulam, penoxsulam, pyroxsulam-   uracil herbicides: benzfendizone, bromacil, butafenacil,    flupropacil, isocil, lenacil, saflufenacil, terbacil-   urea herbicides: benzthiazuron, cumyluron, cycluron, dichloralurea,    diflufenzopyr, isonoruron, isouron, methabenzthiazuron, monisouron,    noruron    -   phenylurea herbicides: anisuron, buturon, chlorbromuron,        chloreturon, chlorotoluron, chloroxuron, daimuron, difenoxuron,        dimefuron, diuron, fenuron, fluometuron, fluothiuron,        isoproturon, linuron, methiuron, methyldymron, metobenzuron,        metobromuron, metoxuron, monolinuron, monuron, neburon,        parafluron, phenobenzuron, siduron, tetrafluron, thidiazuron    -   sulfonylurea herbicides:        -   pyrimidinylsulfonylurea herbicides: amidosulfuron,            azimsulfuron, bensulfuron, chlorimuron, cyclosulfamuron,            ethoxysulfuron, flazasulfuron, flucetosulfuron,            flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron,            mesosulfuron, metazosulfuron, nicosulfuron, orthosulfamuron,            oxasulfuron, primisulfuron, propyrisulfuron, pyrazosulfuron,            rimsulfuron, sulfometuron, sulfosulfuron, trifloxysulfuron        -   triazinylsulfonylurea herbicides: chlorsulfuron,            cinosulfuron, ethametsulfuron, iodosulfuron, metsulfuron,            prosulfuron, thifensulfuron, triasulfuron, tribenuron,            triflusulfuron, tritosulfuron    -   thiadiazolylurea herbicides: buthiuron, ethidimuron,        tebuthiuron, thiazafluron, thidiazuron-   unclassified herbicides: acrolein, allyl alcohol,    aminocyclopyrachlor, azafenidin, bentazone, benzobicyclon,    bicyclopyrone, buthidazole, calcium cyanamide, cambendichlor,    chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol,    cinmethylin, clomazone, CPMF, cresol, cyanamide,    ortho-dichlorobenzene, dimepiperate, endothal, fluoromidine,    fluridone, flurochloridone, flurtamone, fluthiacet, indanofan,    methyl isothiocyanate, OCH, oxaziclomefone, pentachlorophenol,    pentoxazone, phenylmercury acetate, prosulfalin, pyribenzoxim,    pyriftalid, quinoclamine, rhodethanil, sulglycapin, thidiazimin,    tridiphane, trimeturon, tripropindan, tritac.

The foregoing herbicides, and links for a further identification anddescription of the herbicides, can be found athttp://www.alanwood.net/pesticides/class_herbicides.html, which isincorporated herein in its entirety.

The following are the most preferred insecticides for use in theinvention: botanical, carbamate, diamide, fumigant, insect growthregulators, nicotinoid, organochlorine, organophosphorus, phthalimide,pyrazole, pyrethroid, pyrethroid ester, pyrethroid ether,pyrimidinamine, pyrrole, thiazole, thiazolidine, and thiourea.

The following are the most preferred herbicides for use in theinvention: amide, aromatic acid, benzothiazole, carbamate, carbanilate,cyclohexene oxime, dicarboximide, dinitroaniline, dinitrophenol,diphenyl ether, imidazolinone, organophosphorus, oxadiazolone, oxazole,phenoxy, phenylenediamine, pyrazole, pyridine, pyridazinone, quaternaryammonium, thiocarbamate, thiocarbonate, thiourea, triazine, triazinone,triazole, triazolone, triazolopyrimidine, urea, and unclassified.

The following are the most preferred fungicides for use in theinvention: Dithiocarbamates, Nitrial, Benzimidazoles, Dicarboximides,Sterol Inhibitors (SI)/Demethylase Inhibitors (DMI),Carboxamides/Anilides, Strobilurins, Phenylpyrrole, Phynylamide, AromicHydrocarbin, Polyoxin, Pyridinamine, Cyanoimidazole, Carbamate, andPhosphonate.

Example 8 Evaluation of Tetrapolymer Partial Salt as Pesticide Adjuvant

In this test, the effectiveness of the previously describedammonium/sodium tetrapolymer partial salt B as a glyphosate adjuvant wascompared with an aqueous mixture containing 40% by weight of amaleic-itaconic polymer ammonium partial salt, having equimolar amountsof maleic and itaconic moieties, and a pH of about 2 (referred to hereinas “M-I ammonium partial salt”).

Glyphosate test dispersion treatments were prepared as follows, using 50mL of glyphosate dispersion in each treatment:

-   -   Treatment A—glyphosate alone    -   Treatment B—glyphosate+1.0% (v/v) MSO    -   Treatment C—glyphosate+0.50% (v/v) M-I ammonium partial        salt+1.0% (v/v) MSO    -   Treatment D—glyphosate+0.50% (v/v) tetrapolymer salt B+1.0%        (v/v) MSO    -   Treatment E—glyphosate+0.50% (v/v) CS    -   Treatment F—glyphosate+0.50% (v/v) M-I ammonium partial        salt+0.50% (v/v) CS    -   Treatment G—glyphosate+0.50% (v/v) tetrapolymer salt B+0.50%        (v/v) CS    -   Treatment H—glyphosate+0.50% (v/v) tetrapolymer salt B

The glyphosate used in all of the formulations was an isopropylamineglyphosate sold under the designation “Glyphosate Star Gold,” and wasprepared as an aqueous dispersion in a 50 mL tube, using theconventional commercial concentration, namely 32 oz of glyphosate peracre. The other ingredients were mixed with the glyphosate to completethe Treatments. The added materials were M-I ammonium partial salt,methylated seed oil surfactant (MSO), and ChemSurf 90 (CS). The latterproduct is a commercially available aqueous surfactant containing 90%alkylarylpolyoxykane ether, isopropanol and free fatty acids, and ismanufactured by Chemorse, Ltd. of Des Moines, Iowa.

Twenty-four 6.75 inch soil pots were planted with pre-germinated podscontaining two Waterhemp (Amaranthus rudis) plants known to be resistantto glyphosate herbicides. Plants were allowed to reach between 10 and 15cm in height, whereupon they were sprayed with the above Treatmentsusing a hand-held CO2 pressurized cone-nozzle sprayer calibrated todeliver 0.230 mL of Treatment to each pot, which is equivalent to aten-gallon tank mixture sprayed over one acre.

A numerical scale based upon live plant observations was used to gaugethe effectiveness of each Treatment, with 0.0 being no effect and 5.0being completely effective. Three replicate observations were made onday 6 and day 12 after spraying, with the cumulative means of allreplications representing the effectiveness of the correspondingTreatment. The results of this series of tests is set forth in Tables 3and 4 below.

TABLE 1 Example 8, Day 6 Observations Group ID Rep 1 Rep 2 Rep 3 MeanTreatment A 3.0 4.0 0.0 2.3 Treatment B 5.0 4.0 0.5 3.2 Treatment C 3.03.0 0.5 2.2 Treatment D 4.0 4.0 4.0 4.0 Treatment E 5.0 3.0 3.0 3.7Treatment F 4.5 5.0 5.0 4.8 Treatment G 5.0 1.0 3.0 3.0 Treatment H 5.04.0 2.5 3.8

TABLE 2 Example 8, Day 12 Observations Group ID Rep 1 Rep 2 Rep 3 MeanTreatment A 3.0 3.5 0 2.2 Treatment B 5.0 5.0 0.5 3.5 Treatment C 5.02.5 0 2.5 Treatment D 3.5 3.0 5.0 3.8 Treatment E 5.0 3.0 5.0 4.3Treatment F 5.0 5.0 5.0 5.0 Treatment G 5.0 2.5 3.0 3.5 Treatment H 5.05.0 2.5 4.2

As illustrated in the foregoing data, the tetrapolymer products of theinvention provided increase adjuvant activity in almost all instances,as compared with the no-polymer and M-I ammonium partial salt tests.This result was especially evident with Treatments D and F, whereobservations starting on Day 1 presented easily discernible differencesbetween Treatments with and without the tetrapolymer additive.

Example 9 Class I Tetrapolymers as Herbicide Adjuvants

Glufosinate Trial

In this series of tests, commercially available Liberty glufosinateherbicide obtained from Bayer CropScience was supplemented with a T5partial sodium and ammonium salt polymer (pH 2.5) at two differentrates.

Tank mixtures were first made by mixing together 10 gallons of deionizedwater and Liberty herbicide at a rate equal to 29 ounces per acre. Thepolymer was then added at a rate of 0.50% v/v or 1% v/v immediatelybefore spray application.

The liquid herbicide mixtures were targeted at 12-inch tall Waterhemp(Amaranthus rudis) having known resistance to glyphosate and triazineherbicides. All treatments were applied at 10 gal/acre using a teejet8002 EVS nozzle in a DeVries Research Sprayer, at a rate of 29 fl. oz.per acre of Liberty herbicide. After 15 days, the percent by weight ofremaining biomass for each plant was measured. The control (no polymer)exhibited 45% remaining biomass, whereas the 0.5% tetrapolymer test gave20% remaining biomass, and the 1% tetrapolymer test gave 10% remainingbiomass.

Dicamba Trial

In this series of tests, commercially available Clarity Dicambaherbicide obtained from BASF Corporation was supplemented with a T5partial sodium salt polymer (pH 8.0) at two different rates.

Tank mixtures were first made by mixing together 10 gallons of deionizedwater and Clarity herbicide at a rate equal to 16 ounces per acre. Thepolymer was then added at a rate of 0.50% v/v or 1% v/v immediatelybefore spray application.

The liquid herbicide mixtures were targeted at Marestail (Conyzacanadensis) at full rosette stage having known resistance to glyphosateherbicides. All treatments were applied at 10 gal/acre using a teejet8002 EVS nozzle in a DeVries Research Sprayer, at a rate of 16 fl. oz.per acre of Clarity herbicide. After 7 days, the percent by weight ofremaining biomass for each plant was measured. The control (no polymer)exhibited 65% remaining biomass, whereas the 0.5% tetrapolymer test gave45% remaining biomass, and the 1% tetrapolymer test gave 50% remainingbiomass. After 14 days, the control had 20% remaining biomass, the 0.5%tetrapolymer test gave 5% remaining biomass, and the 1% tetrapolymertest gave 15% remaining biomass.

2,4-D Trial

In this series of tests, commercially available 2,4-D diethylamine saltherbicide was supplemented with a T5 partial sodium and ammonium saltpolymer (pH 2.5) at two different rates.

Tank mixtures were first made by mixing together 10 gallons of deionizedwater and 2,4-D herbicide at a rate equal to 32 ounces per acre. Thepolymer was then added at a rate of 0.50% v/v or 1% v/v immediatelybefore spray application.

The liquid herbicide mixtures were targeted at Marestail (Conyzacanadensis) at full rosette stage having known resistance to glyphosateherbicides. All treatments were applied at 10 gal/acre using a teejet8002 EVS nozzle in a DeVries Research Sprayer, at a rate of 32 fl. oz.per acre of herbicide. After 7 days, the percent by weight of remainingbiomass for each plant was measured. The control (no polymer) exhibited70% remaining biomass, whereas the 0.5% tetrapolymer test gave 60%remaining biomass, and the 1% tetrapolymer test gave 65% remainingbiomass. After 14 days, the control had 25% remaining biomass, the 0.5%tetrapolymer test gave 10% remaining biomass, and the 1% tetrapolymertest gave 15% remaining biomass.

10. Nitrification/Urease/Phosphate Fixation Inhibition

The Class I polymers of the invention have also been found to serve asuseful inhibitors for the nitrification processes within soil, and toalso inhibit phosphate fixation and urease activities therein. In thisfashion, increased crop yields are realized owing to the fact thatnaturally occurring and fertilizer-supplied nitrogen and phosphatesources are more efficiently utilized by plants. The polymers of theinvention may be applied directly to soil in aqueous dispersion or solidform and in amounts effective for controlling nitrification, ureaseactivity, and phosphate fixation; more commonly, however, the polymersare used in conjunction with solid ammoniacal fertilizer (e.g., urea),or with fluid fertilizers (e.g., gaseous fertilizers or liquid UAN)containing ammoniacal nitrogen.

As used herein, “ammoniacal nitrogen” is a broad term embracingfertilizer compositions containing ammoniacal nitrogen (NH₄) as well asfertilizer compositions and other compounds which are precursors ofammoniacal nitrogen or that cause ammoniacal nitrogen to be generatedwhen the fertilizers or compounds undergo various reactions such ashydrolysis. To give but one example, the polymers of the invention maybe applied to or mixed with urea or other nitrogen-containingfertilizers which have no ammoniacal nitrogen therein as such.Nonetheless, such fertilizers will undergo reactions in the soil togenerate ammoniacal nitrogen in situ. Thus, in this example urea orother precursor nitrogen-containing fertilizers would be deemed tocontain ammoniacal nitrogen.

When the Class I polymers are used in the form of aqueous dispersions inintimate contact with or dispersed in ammoniacal nitrogen fertilizers,the polymer/fertilizer mixture is typically applied to soil adjacentgrowing plants or pre-applied to soils subject to nitrification. Aqueouspolymer mixtures are typically used with liquid and dry fertilizers atrelatively low levels up to about 2% by volume (e.g., 0.01-2% by volume)based upon the total volume of the liquid fertilizer material taken as100% by volume. In such uses, it is also preferred that the pH levelsshould be up to about 3, more preferably up to about 2, and mostpreferably up to about 1. Moreover, such aqueous dispersionsadvantageously contain from about 10-85% by weight solids, morepreferably from about 30-65% by weight solids, and most preferably about40% by weight solids.

In preparing the polymer/liquid fertilizer materials of the invention,the ammoniacal nitrogen-containing fertilizer material(s) are suspendedin water and the aqueous polymer mixture(s) are added thereto withmixing. No particular mixing regime or temperature conditions arerequired. Surprisingly, it has been found that these liquid fertilizermaterials are quite stable and resist settling out or precipitation ofsolids over extended storage periods of at least about two weeks.

In the case of solid ammoniacal fertilizers, the polymers are directlyapplied to the fertilizer, typically at a level of from about 0.01-10%by weight, more preferably from about 0.05-2% by weight, based upon thetotal weight of the polymer/fertilizer product taken as 100% by weight.Normally, aqueous dispersions of the polymer are sprayed onto the solidfertilizers and allowed to dry, so that the polymeric dried residueremains on the surfaces of the fertilizers

Example 10 Evaluation of Tetrapolymer Partial Salt as UreaseInhibitor—Method 1

Studies have shown that urea-containing fertilizers can lose up to 30%or more of their N if not incorporated into soil within 72 hours bytillage or rainfall. Volatilization occurs when urea hydrolyzes, i.e.,it reacts with soil moisture and breaks down. The enzyme urease, whichis produced by soil microorganisms, facilitates volatilization.Therefore, best management practices dictate that urease be inhibited tothe extent possible.

In this test, the urease inhibition effectiveness of the tetrapolymersof the invention was determined, as compared with prior artmaleic-itaconic partial salts. In the test, 50 mL Erlenmeyer flasks werecharged with 25 mL of 1.0% (w/w) stock urea dispersion, and two levelsof tetrapolymer salt B, namely 0.033% (v/v) (8.25 μL) and 0.066% (v/v)(16.5 μL). Comparative flasks were also prepared containing the sameamounts of urea dispersion, but with a 40% solids aqueous dispersion ofa partial calcium salt of a maleic-itaconic polymer containing equimolaramounts of maleic and itaconic moieties, and having a pH of from about2.25-2.75, nominally 2.5 (referred to herein as “M-I Ca 2.5”) and a 40%solids aqueous dispersion of a partial calcium salt of a maleic-itaconicpolymer containing equimolar amounts of maleic and itaconic moieties,and having a pH of from about 1-2, nominally 1.5 (referred to herein as“M-I Ca 1.5”). Control flasks containing no urease inhibition polymerwere also prepared.

A pH meter and electrode were used to record initial pH levels,whereupon an additional 1.0% (v/v) of urease enzyme dispersion was addedto each flask. pH measurements were taken at timed intervals to trackthe breakdown of urea in the flasks. As the urea breaks down, ammoniaions are generated, causing a subsequent rise in the pH of thedispersions. By observing the rate of pH elevation, the effectiveness ofurease inhibition can be measured.

TABLE 1 Example 10, Trial 1: Urease Inhibition with 0.033% InhibitorPolymer Salt M-I Ca M-I Ca Salt B 2.5 1.5 Control Initial pH 4.122 4.0843.088 7.000 30 Second pH 8.400 4.818 3.362 9.295 (immediate) 120 SecondpH 9.105 8.389 3.753 600 Second pH x x 6.484 Increase (600 s) 4.9834.305 3.396

TABLE 2 Example 10, Trial 1: Urease Inhibition with 0.066% InhibitorPolymer Salt M-I Ca M-I Ca Salt B 2.5 1.5 Control Initial pH 3.943 3.9083.496 7.000 30 Second pH 4.087 4.055 3.559 9.295 (immediate) 120 SecondpH 4.601 4.345 3.801 600 Second pH 9.305 6.504 4.636 Increase (600 s)5.362 2.596 1.14 

As illustrated, the control flasks without any polymeric ureaseinhibitor exhibited an immediate pH spike. However, the tetrapolymersalts of the invention gave functional urease inhibition results ascompared with the prior art M-I Ca 2.5 and M-I Ca 1.5 products,particularly at the higher usage rate of Table 6.

Example 11 Evaluation of Tetrapolymer Partial Salt as UreaseInhibitor—Method 2

In this test, the urease inhibition properties of the tetrapolymers ofthe invention were determined as compared with the prior art M-I Ca 2.5and M-I Ca 1.5 products, using a different technique. In particular,nine 50 mL Erlenmeyer flasks were charged with 25 mL each of deionizedwater, to give three flask sets A, B, and C, each set containing threeflasks. Thereupon, 0.033% (v/v) of the M-I Ca 2.5, M-I Ca 1.5, and saltB polymers were individually added to the three flasks of each set.After the pH levels of the flasks containing water and polymerstabilized, 1% (v/v) urease dispersion was added to each of the nineflasks, and the individual flasks containing water/polymer/urease wereallowed to incubate for three different time periods, namely 1 (set A),3 (set B), and 10 (set C) minutes. The pH levels were taken at thispoint, followed by adding 0.5 mL of 50% (w/w) urea-water dispersion toeach flask to obtain a total of 1% (w/w) of urea in each flaskdispersion. pH measurements were then observed at time intervals of 30seconds, 120 seconds, and 600 seconds. As the urea broke down in eachflask, ammonia was released, causing a rise in pH in the dispersions. Byobserving the rate of pH rise, the effectiveness of urease inhibitionwas measured; this rate is directly affected by the amount of incubationtime between the three sets.

TABLE 1 Example 11, One Minute Incubation of Polymer/Urease - Set A SaltM-I Ca M-I Ca Polymer B 2.5 1.5 Initial pH, H2O and polymer 3.974 3.8563.588 H2O, Polymer, and Urease 3.895 3.789 3.523 after one minute 30 safter adding urea 4.194 4.003 3.695 dispersion 120 seconds 4.510 4.3533.763 600 seconds 7.934 8.907 6.176

TABLE 2 Example 11, Three Minute Incubation of Polymer/Urease - Set BSalt M-I Ca M-I Ca Polymer B 2.5 1.5 Initial pH, H2O and polymer 3.9253.951 3.619 H2O, Polymer, and Urease 4.025 3.845 3.559 after one minute30 s after adding urea 4.025 3.975 3.690 dispersion 120 seconds 4.2604.043 3.761 600 seconds 4.765 7.663 3.934

TABLE 3 Example 11, Ten Minute Incubation of Polymer/Urease - Set C SaltM-I Ca M-I Ca Polymer B 2.5 1.5 Initial pH, H2O and polymer 3.987 3.832H2O, Polymer, and Urease 3.908 3.756 after one minute 30 s after addingurea 4.049 3.848 dispersion 120 seconds 4.081 3.879 600 seconds 4.1403.951

Example 12 Class I Polymer as Urease Enzyme Inhibitor

In a first series of tests, 25 mL aliquots of 1% (w/w) stock ureasolution were combined in 50 mL Erlenmeyer flasks with four differenttest formulations at equal levels of 0.666% (v/v). A pH meter andelectrode were used to record initial pH levels, and then 1.0% (v/v)urease solution was added to each flask. pH measurements over time (at30 seconds, 120 seconds, and 600 seconds) were observed as a measure ofurea breakdown, generating ammonia and consequently causing a rise in pHlevels. The rates of pH rise were a measure of the effectiveness ofurease inhibition. Two replications A and B were carried out for eachtest formulation.

The test formulations were:

-   -   No. 1—no polymer, 4% w/w boric acid, 30% w/w lactic acid,        balance water, with added dye.    -   No. 2—T5 polymer as a mixed sodium/calcium partial salt in        water, pH about 1.    -   No. 3—34% w/w T5 polymer as a mixed calcium/sodium partial salt,        4% w/w boric acid, 1.5% w/w low molecular weight polyvinyl        alcohol, 22% w/w lactic acid, no dye, with the balance being        water, pH of about 1.    -   No. 4—T5 polymer as a mixed sodium/calcium partial salt in        water, pH about 1, with 4.3% w/w boric acid, and 32% w/w lactic        acid.        The results of this first series of tests are set forth below.

TABLE 1 Example 12 Test Formulation Replication Initial pH 30 s pH 120 spH 600 s pH 1 A 3.31 4.40 8.99 9.08 1 B 3.37 4.04 8.99 9.14 2 A 3.433.30 3.37 3.64 2 B 3.36 3.27 3.33 3.73 3 A 3.09 3.03 3.08 3.21 3 B 3.253.18 3.22 3.23 4 A 3.16 3.12 3.10 3.10 4 B 3.21 3.20 3.21 3.44As illustrated in the foregoing data, test formulations containing ClassI tetrapolymers without boric acid both gave sustained disablement ofurease enzyme. Further testing has confirmed that the Class Itetrapolymers inhibit urease completely through 10 minutes.

In a second series of tests, the same formulation Nos. 1-4 were testedunder a different procedure. Specifically, 24.5 mL of water was combinedwith the test formulations in 50 mL Erlenmeyer flasks to obtain a testformulation level of 0.033% v/v. Immediately thereafter, urease enzymewas added to each flask at a rate of 1.0% v/v, and allowed to incubatefor 60 seconds or 300 seconds. Once the incubations were complete,initial pH measurements were taken and 0.5 mL of 50% w/w urea solutionwas added to each flask to bring the total solutions to 1% w/w of ureaand water. Thereafter, pH measurements were taken at 60 seconds/300seconds, 90 seconds/330 seconds, 180 seconds/400 seconds, and 600seconds/900 seconds. Furthermore, ambient air ammonia concentrationsfrom the respective flasks were measured after 4 hours as anotherindicator of urease inhibition. The results of this test are set forthbelow.

TABLE 2 Example 12 Incubation Test Period/ Wait Wait Wait NH3/ Formu-Initial Time/ Time/ Time/ 4 lation pH pH pH pH hours 1 60 s/3.93 90s/8.99 180 s/9.25 660 s/9.29 290 ppm 1 300 s/4.05  330 s/9.04  420s/9.14 900 s/9.22 220 ppm 2 60 s/4.72 90 s/6.26 180 s/7.67 660 s/8.95  9ppm 2 300 s/4.34  330 s/6.71  420 s/8.11 900 s/8.84  9 ppm 3 60 s/3.9790 s/5.74 180 s/8.40 660 s/9.09  20 ppm 3 300 s/4.14  330 s/5.90  420s/6.36 900 s/7.08  9 ppm 4 60 s/3.85 90 s/4.94 180 s/7.97 660 s/9.06  24ppm 4 300 s/3.88  330 s/5.28  420 s/6.94 900 s/8.50  9 ppm

Example 13 Class I Tetrapolymers as Phosphorous Fixation Inhibitors

Phosphorous fertilizer can become tied-up or fixed with antagonisticcations in soils, which results in 75-95% of applied phosphorousbecoming unavailable for plant uptake. It has been found that the ClassI polymers of the invention are capable of reducing such phosphorousfixation by sequestration of antagonistic cations in themicroenvironments of phosphorous fertilizers.

In a field test, two rates of phosphorous as diammonium phosphate (DAP)were broadcast-applied as a pre-plant fertilizer to a cotton field,namely 65 lbs of DAP per acre and 130 lbs of DAP per acre. The testswere two replications each of an unfertilized control, a DAP-onlycontrol, and DAP mixed with 0.25% w/w of a Class I polymer formulation.The formulation included 40% w/w of a partial zinc/sodium salt of T5polymer, 5% w/w zinc, and the balance water, pH about 3,

Tissue tests were taken prior to first bloom from each plot, and thepercent of phosphorous in the plant tissue was measured. Afterharvesting, lint yields were measured. The tissue phosphorous testresults are set forth below in Table 1, whereas the yield tests aregiven in Table 2.

TABLE 1 Example 13 % by weight Phosphorous Treatment in Tissueunfertilized control 0.21 65 lbs DAP 0.41 65 lbs DAP w/polymer 0.5unfertilized control 0.21 130 lbs DAP 0.41 130 lbs DAP w/polymer 0.51

TABLE 2 Example 13 Treatment Lint Yield lbs/acre unfertilized control390 65 lbs DAP 712 65 lbs DAP w/polymer 896 unfertilized control 390 130lbs DAP 781 130 lbs DAP w/polymer 900These results confirm that the use of the Class I tetrapolymer with zincgave a significant increase in tissue phosphorous levels and yields.

The foregoing Examples 5-13 illustrate specific uses of the novel ClassI polymers of the invention in various contexts. It is to be understoodthat these Examples are provided by way of illustration only, andnothing therein should be taken as a limitation upon the overall scopeof the invention.

1-208. (canceled)
 209. An agricultural product comprising fertilizer anda polymer mixed with the fertilizer, said polymer being an anionicpolymer comprising at least four repeat units distributed along thelength of the polymer chain, said repeat units including at least oneeach of a maleic, itaconic, and sulfonate repeat unit.
 210. Theagricultural product of claim 209, said polymer being a tetrapolymer andhaving maleic and itaconic repeat units, and two different sulfonaterepeat units.
 211. The product of claim 209, said fertilizer being solidfertilizer, said polymer applied to said fertilizer as a liquiddispersion.
 212. The product of claim 209, said fertilizer being inliquid form, said polymer mixed with said liquid fertilizer.
 213. Theproduct of claim 209, said fertilizer selected from the group consistingof starter fertilizers, phosphate-based fertilizers, fertilizerscontaining nitrogen, phosphorus, potassium, calcium, magnesium, boron,zinc, manganese, copper, or molybdenum materials, and compounds selectedfrom the group consisting of gypsum, one or more members of theKieserite Group, potassium magnesium sulfate, elemental sulfur, andmixtures thereof.
 214. The product of claim 209, said polymer beingpresent at a level of from about 0.001-20 g per 100 g of saidfertilizer.
 215. The product of claim 209, said polymer being incombination with another anionic polymer including maleic and itaconicrepeat units.
 216. A method of fertilizing soil comprising the step ofapplying the product of claim 209 to soil.
 217. An agricultural productincluding a polymer in combination with a fertilizer, said polymer beingan anionic polymer comprising at least four repeat units distributedalong the length of the polymer chain, said at least four repeat unitsincluding at least one each of type B, type C, and type G repeat units,said type B repeat units selected from the group consisting of repeatunits derived from substituted and unsubstituted monomers of maleic acidand/or anhydride, fumaric acid and/or anhydride, mesaconic acid and/oranhydride, mixtures of the foregoing, and any isomers, esters, acidchlorides, and partial or complete salts of any of the foregoing,wherein type B repeat units may be substituted with one or more C1-C6straight or branched chain alkyl groups substantially free of ringstructures and halo atoms, and wherein the salts have salt-formingcations selected from the group consisting of metals, amines, andmixtures thereof, said type C repeat units selected from the groupconsisting of repeat units derived from substituted or unsubstitutedmonomers of itaconic acid, itaconic anhydride, and any isomers, esters,and the partial or complete salts of any of the foregoing, and mixturesof any of the foregoing, wherein the type C repeat units may besubstituted with one or more C1-C6 straight or branched chain alkylgroups substantially free of ring structures and halo atoms, and whereinthe salts have salt-forming cations selected from the group consistingof metals, amines, and mixtures thereof, said type G repeat unitsselected from the group consisting of repeat units derived fromsubstituted or unsubstituted sulfonated monomers possessing at least onecarbon-carbon double bond and at least one sulfonate group and which aresubstantially free of aromatic rings and amide groups, and any isomers,and the partial or complete salts of any of the foregoing, and mixturesof any of the foregoing, wherein type G repeat units may be substitutedwith one or more C1-C6 straight or branched chain alkyl groupssubstantially free of ring structures and halo atoms, and wherein thesalts of the type G repeat units have salt-forming cations selected fromthe group consisting of metals, amines, and mixtures thereof, saidanionic polymer containing no more than about 10 mole percent ofnon-carboxylate olefins and/or ethers.
 218. The agricultural product ofclaim 217, said polymer being a tetrapolymer and having maleic anditaconic repeat units, and two different sulfonate repeat units. 219.The product of claim 217, said fertilizer being solid fertilizer, saidpolymer applied to said fertilizer as a liquid dispersion.
 220. Theproduct of claim 217, said fertilizer being in liquid form, said polymermixed with said liquid fertilizer.
 221. The product of claim 217, saidfertilizer selected from the group consisting of starter fertilizers,phosphate-based fertilizers, fertilizers containing nitrogen,phosphorus, potassium, calcium, magnesium, boron, zinc, manganese,copper, or molybdenum materials, and compounds selected from the groupconsisting of gypsum, one or more members of the Kieserite Group,potassium magnesium sulfate, elemental sulfur, and mixtures thereof.222. The product of claim 217, said polymer being present at a level offrom about 0.001-20 g per 100 g of said fertilizer.
 223. The product ofclaim 217, said polymer being in combination with another anionicpolymer including maleic and itaconic repeat units.
 224. A method offertilizing soil comprising the step of applying the product of claim217 to soil.
 225. A method comprising the step of applying to plants,the leaves of plants, the seeds of plants, or the earth adjacent plants,an effective amount of a polymer, said polymer being an anionic polymercomprising at least four repeat units distributed along the length ofthe polymer chain, said repeat units including at least one each of amaleic, itaconic, and sulfonate repeat unit.
 226. The method of claim225, said polymer being a tetrapolymer and having maleic and itaconicrepeat units, and two different sulfonate repeat units.
 227. The methodof claim 225, said fertilizer being in liquid form, said polymer mixedwith said liquid fertilizer.
 228. The method of claim 225, saidfertilizer being in solid form, said polymer applied to the surface ofthe solid fertilizer.
 229. The method of claim 225, said fertilizerselected from the group consisting of phosphate-based fertilizers,fertilizers containing nitrogen, phosphorus, potassium, calcium,magnesium, boron, zinc, manganese, copper, or molybdenum materials, andcompound selected from the group consisting of gypsum, one or moremembers of the Kieserite Group, potassium magnesium sulfate, elementalsulfur, and mixtures thereof.
 230. The method of claim 225, said polymerbeing present at a level of from about 0.001-20 g per 100 g of saidfertilizer.
 231. A method comprising the step of applying to plants, theleaves of plants, the seeds of plants, or the earth adjacent plants, aneffective amount of a polymer, said polymer being an anionic polymercomprising at least four repeat units distributed along the length ofthe polymer chain, said at least four repeat units including at leastone each of type B, type C, and type G repeat units, said type B repeatunits selected from the group consisting of repeat units derived fromsubstituted and unsubstituted monomers of maleic acid and/or anhydride,fumaric acid and/or anhydride, mesaconic acid and/or anhydride, mixturesof the foregoing, and any isomers, esters, acid chlorides, and partialor complete salts of any of the foregoing, wherein type B repeat unitsmay be substituted with one or more C1-C6 straight or branched chainalkyl groups substantially free of ring structures and halo atoms, andwherein the salts have salt-forming cations selected from the groupconsisting of metals, amines, and mixtures thereof, said type C repeatunits selected from the group consisting of repeat units derived fromsubstituted or unsubstituted monomers of itaconic acid, itaconicanhydride, and any isomers, esters, and the partial or complete salts ofany of the foregoing, and mixtures of any of the foregoing, wherein thetype C repeat units may be substituted with one or more C1-C6 straightor branched chain alkyl groups substantially free of ring structures andhalo atoms, and wherein the salts have salt-forming cations selectedfrom the group consisting of metals, amines, and mixtures thereof, saidtype G repeat units selected from the group consisting of repeat unitsderived from substituted or unsubstituted sulfonated monomers possessingat least one carbon-carbon double bond and at least one sulfonate groupand which are substantially free of aromatic rings and amide groups, andany isomers, and the partial or complete salts of any of the foregoing,and mixtures of any of the foregoing, wherein type G repeat units may besubstituted with one or more C1-C6 straight or branched chain alkylgroups substantially free of ring structures and halo atoms, and whereinthe salts of the type G repeat units have salt-forming cations selectedfrom the group consisting of metals, amines, and mixtures thereof, saidanionic polymer containing no more than about 10 mole percent ofnon-carboxylate olefins and/or ethers.
 232. The method of claim 231,said polymer being a tetrapolymer and having maleic and itaconic repeatunits, and two different sulfonate repeat units.
 233. The method ofclaim 231, said fertilizer being in liquid form, said polymer mixed withsaid liquid fertilizer.
 234. The method of claim 231, said fertilizerbeing in solid form, said polymer applied to the surface of the solidfertilizer.
 235. The method of claim 231, said fertilizer selected fromthe group consisting of phosphate-based fertilizers, fertilizerscontaining nitrogen, phosphorus, potassium, calcium, magnesium, boron,zinc, manganese, copper, or molybdenum materials, and compound selectedfrom the group consisting of gypsum, one or more members of theKieserite Group, potassium magnesium sulfate, elemental sulfur, andmixtures thereof.
 236. The method of claim 231, said polymer beingpresent at a level of from about 0.001-20 g per 100 g of saidfertilizer.